Processes for producing chlorinated hydrocarbons and methods for recovering polyvalent antimony catalysts therefrom

ABSTRACT

The preparation of chlorinated hydrocarbons, such as pentachloropropanes, such as 1,1,1,2,3-pentachloropropane, from tetrachloropropanes, such as 1,1,1,3-tetrachloropropane, in the presence of a polyvalent antimony compound that includes a pentavalent antimony compound, such as antimony pentachloride, is described. Also described are methods for preparing optionally chlorinated alkenes, such as, tetrachloropropenes, from chlorinated alkanes, such as pentachloropropanes, in the presence of polyvalent antimony compound that includes a pentavalent antimony compound, as well as methods for recovering polyvalent antimony compounds from such processes.

CROSS REFERENCE TO RELATED PATENT APPLICATIONS

This application is a continuation of U.S. patent application Ser. No.15/041,409, filed on Feb. 11, 2016, which is a divisional of Ser. No.14/521,449, filed Oct. 22, 2014, now U.S. Pat. No. 9,289,758, which is acontinuation-in-part of U.S. patent application Ser. No. 14/060,957,filed Oct. 23, 2013, now U.S. Pat. No. 8,889,930, which claims thebenefit of U.S. Patent Application No. 61/755,062, filed on Jan. 22,2013, and U.S. Patent Application No. 61/789,786, filed on Mar. 15,2013, the disclosures of each of which are incorporated herein byreference in their entireties.

BACKGROUND OF THE INVENTION

Field of the Invention

The present invention relates to methods for recovering polyvalentantimony catalyst(s) from a halohydrocarbon chlorination or crackingprocess for reuse as a catalyst in the chlorination of halohydrocarbonsor cracking of halohydrocarbons.

Description of the Related Art

Chlorinated hydrocarbons are useful as feedstocks for the manufacture offluorinated hydrocarbons, such as hydrofluoroolefins (HFOs).Hydrofluoroolefins can, for example, be used as, or as components of,refrigerants, polyurethane blowing agents, fire extinguishing agents,and foaming agents. For purposes of illustration,1,1,1,2,3-pentachloropropane can be used as an intermediate in themanufacture of 1,1,2,3-tetrachloropropene, which is a feedstock for thepreparation of HFOs, and in the preparation of the herbicidetrichloroallyl diisopropyl thiocarbamate, which is commonly referred toas Triallate.

The preparation of chlorinated hydrocarbons typically involves reactionsthat can require a number of steps, extended periods of time tocomplete, and/or reduced reaction temperatures and related refrigerationequipment, which can have increased economic costs associated therewith.It would be desirable to develop new methods of forming chlorinatedhydrocarbons that require less steps and/or reduced reaction timesrelative to existing methods.

Antimony trichloride and antimony pentachloride can be used as catalystsin the chlorination of hydrocarbons and the cracking of halohydrocarbonsto prepare olefins or haloolefins. However, the removal of the antimonycompounds from the desired products can be very complicated and costlydue to their solubilities and volatilities. Antimony removal techniques,such as acidic or basic washes, carbon filtration, adsorption ontoalumina and silica, etc., render the antimony catalysts unusable forprocess recycling. It is desirable to recover the antimony compounds forrecycle or reuse in chlorination and cracking processes.

SUMMARY

In some embodiments, there is provided a method of forming an alkeneproduct comprising, heating a chlorinated alkane substrate in thepresence of at least one polyvalent antimony compound comprising atleast one pentavalent antimony compound, thereby forming a productcomprising said alkene product, wherein said alkene product optionallyhas at least one chlorine group covalently bonded thereto, and saidchlorinated alkane substrate and said alkene product each have a carbonbackbone structure that is in each case the same.

In some embodiments, there is provided a method of preparing1,1,1,2,3-pentachloropropane comprising, reacting1,1,1,3-tetrachloropropane with a source of chlorine in the presence ofa polyvalent antimony compound comprising a pentavalent antimonycompound and substantially free of iron chloride, iron metal, and/ortrialkylphosphate, thereby forming a product comprising1,1,1,2,3-pentachloropropane.

In some embodiments, there is provided a method of forming1,1,3,3-tetrachloropropene comprising heating1,1,1,3,3-pentachloropropane in the presence of at least one polyvalentantimony compound comprising at least one pentavalent antimony compound,thereby forming 1,1,3,3-tetrachloropropene.

In some embodiments, there is provided a method of recycling at leastone polyvalent antimony catalyst from a product of a chloroalkanedehydrochlorination process, comprising: (a) providing a productcomprising 1,1,3,3-tetrachloropropene, 1,1,1,3,3-pentachloropropane andat least one polyvalent antimony catalyst, and optionally1,1,1,2,3-pentachloropropane; (b) optionally converting the polyvalentantimony catalyst to trivalent antimony catalyst to form a productcomprising 1,1,3,3-tetrachloropropene, 1,1,1,3,3-pentachloropropane, andat least one trivalent antimony catalyst; (c) separating at least aportion of the 1,1,3,3-tetrachloropropene from: (i) the product of step(a) comprising 1,1,3,3-tetrachloropropene, 1,1,1,3,3-pentachloropropane,and at least one polyvalent antimony catalyst; or (ii) the product ofstep (b) comprising 1,1,3,3-tetrachloropropene,1,1,1,3,3-pentachloropropane, and at least one trivalent antimonycatalyst by distillation; and (d) recycling: (i) a remaining portion ofthe product of step (c)(i) comprising 1,1,1,3,3-pentachloropropane andthe at least one polyvalent antimony catalyst; or (ii) a remainingportion of the product of step (c)(ii) comprising1,1,1,3,3-pentachloropropane and the at least one trivalent antimonycatalyst by distillation; and to a chloroalkane chlorination process ora chloroalkane dehydrochlorination process.

In some embodiments, there is provided a method of preparing1,1,3,3-tetrachloropropene by chloroalkane dehydrochlorination process,the method comprising: (a) reacting 1,1,1,3,3-pentachloropropane in thepresence of at least one polyvalent antimony catalyst in a reactionvessel, thereby forming a crude product comprising1,1,3,3-tetrachloropropene, a portion of the1,1,1,3,3-pentachloropropane and the at least one polyvalent antimonycatalyst; and (b) optionally converting the polyvalent antimony catalystto trivalent antimony catalyst to form a product comprising1,1,3,3-tetrachloropropene, 1,1,1,3,3-pentachloropropane, and at leastone trivalent antimony catalyst; (c) separating at least a portion ofthe 1,1,3,3-tetrachloropropene from: (i) the product of step (a)comprising 1,1,3,3-tetrachloropropene, 1,1,1,3,3-pentachloropropane, andat least one polyvalent antimony catalyst; or (ii) the product of step(b) comprising 1,1,3,3-tetrachloropropene, 1,1,1,3,3-pentachloropropane,and at least one trivalent antimony catalyst by distillation; and (d)recycling: (i) a remaining portion of the product of step (c)(i)comprising 1,1,1,3,3-pentachloropropane, and the at least one polyvalentantimony catalyst; or (ii) a remaining portion of the product of step(c)(ii) comprising 1,1,1,3,3-pentachloropropane, and the at least onetrivalent antimony catalyst by distillation; and back to thechloroalkane dehydrochlorination process.

In some embodiments, there is provided a method of recycling at leastone polyvalent antimony catalyst from a product of a chloroalkanedehydrochlorination process, comprising: (a) providing a productcomprising at least one chlorinated alkene product, at least onechlorinated alkane product, and at least one polyvalent antimonycatalyst, the at least one chlorinated alkene product having a boilingpoint at least about 5° C. less than the at least one chlorinated alkaneproduct at about 1 atmosphere pressure; (b) optionally converting thepolyvalent antimony catalyst to trivalent antimony catalyst to form aproduct comprising at least one chlorinated alkene product, at least onechlorinated alkane product, and at least one trivalent antimonycatalyst; (c) separating at least a portion of the at least onechlorinated alkene product from: (i) the product of step (a) comprisingat least one chlorinated alkene product, at least one chlorinated alkaneproduct, and at least one polyvalent antimony catalyst; or (ii) theproduct of step (b) comprising the at least one chlorinated alkeneproduct, at least one chlorinated alkane product, and at least onetrivalent antimony catalyst by distillation; and (d) recycling: (i) aremaining portion of the product of step (c)(i) comprising at least onechlorinated alkane product, and the at least one polyvalent antimonycatalyst; or (ii) a remaining portion of the product of step (c)(ii)comprising the at least one chlorinated alkane product, and the at leastone trivalent antimony catalyst by distillation; and to a chloroalkanechlorination process or a chloroalkane dehydrochlorination process.

In some embodiments, there is provided a method of preparing achlorinated alkene product by chloroalkane dehydrochlorination process,the method comprising: (a) reacting at least one chlorinated alkane inthe presence of at least one polyvalent antimony catalyst in a reactionvessel, thereby forming a crude product comprising at least onechlorinated alkene product, a portion of the at least one chlorinatedalkane and the at least one polyvalent antimony catalyst, the at leastone chlorinated alkene product having one less chloro group (or chlorineatom) covalently bonded thereto and one less hydrogen atom covalentlybonded thereto than the at least one chlorinated alkane, the at leastone chlorinated alkane and the at least one chlorinated alkene producthaving a carbon backbone structure that is in each case the same, the atleast one chlorinated alkene product having a boiling point at leastabout 5° C. less than the at least one chlorinated alkane; and (b)optionally converting the polyvalent antimony catalyst to trivalentantimony catalyst to form a product comprising at least one chlorinatedalkene product, at least one chlorinated alkane, and at least onetrivalent antimony catalyst; (c) separating at least a portion of the atleast one chlorinated alkene product from: (i) the product of step (a)comprising at least one chlorinated alkene product, at least onechlorinated alkane, and at least one polyvalent antimony catalyst; or(ii) the product of step (b) comprising the at least one chlorinatedalkene product, at least one chlorinated alkane, and at least onetrivalent antimony catalyst by distillation; and (d) recycling: (i) aremaining portion of the product of step (c)(i) comprising at least onechlorinated alkane, and the at least one polyvalent antimony catalyst;or (ii) a remaining portion of the product of step (c)(ii) comprisingthe at least one chlorinated alkane, and the at least one trivalentantimony catalyst by distillation; and back to the chloroalkanedehydrochlorination process.

In some embodiments, a method for separating a portion of at least onechlorinated alkane product from a product comprising at least onepentavalent antimony catalyst, at least one chlorinated alkane carriercompound, and at least one chlorinated alkane product is provided, themethod comprising: (a) providing a product comprising at least onepentavalent antimony catalyst, at least one chlorinated alkane carriercompound having a boiling point between about 170° C. and about 250° C.at about 1 atmosphere pressure, and at least one chlorinated alkaneproduct having a boiling point at least about 5° C. less than the atleast one chlorinated carrier compound at about 1 atmosphere pressure;(b) converting the pentavalent antimony catalyst to trivalent antimonycatalyst to form a product comprising at least one trivalent antimonycatalyst, at least one chlorinated alkane carrier compound, and at leastone chlorinated alkane product; (c) separating at least a portion of theat least one chlorinated alkane product from the product comprising theat least one trivalent antimony catalyst, the at least one chlorinatedalkane carrier compound, and any remainder of the at least onechlorinated alkane product by distillation.

In some embodiments, a method of recycling at least one polyvalentantimony catalyst from a product of a chlorination process is provided,the method comprising: (a) providing a product comprising at least onepentavalent antimony catalyst, at least one chlorinated alkane carriercompound having a boiling point between about 170° C. and about 250° C.at about 1 atmosphere pressure, and at least one chlorinated alkaneproduct having a boiling point at least about 5° C. less than the atleast one chlorinated carrier compound at about 1 atmosphere pressure;(b) converting the pentavalent antimony catalyst to trivalent antimonycatalyst to form a product comprising at least one trivalent antimonycatalyst, at least one chlorinated alkane carrier compound, and at leastone chlorinated alkane product; (c) separating at least a portion of theat least one chlorinated alkane product from the product comprising theat least one trivalent antimony catalyst, the at least one chlorinatedalkane carrier compound, and any remainder of the at least onechlorinated alkane product by distillation; and (d) recycling theproduct comprising the at least one trivalent antimony catalyst, the atleast one chlorinated alkane carrier compound, and any remainder of theat least one chlorinated alkane product to a chlorination process.

In some embodiments, a method of further chlorinating at least onechlorinated alkane substrate, comprising: (a) reacting in a reactionvessel at least one chlorinated alkane substrate with a source ofchlorine in the presence of at least one pentavalent antimony catalystand at least one chlorinated alkane carrier compound having a boilingpoint between about 170° C. and about 250° C. at about 1 atmospherepressure, thereby forming a product comprising at least one chlorinatedalkane product, the at least one chlorinated alkane carrier compound,and the at least one pentavalent antimony catalyst, the chlorinatedalkane product having covalently bonded thereto at least one more chlorogroup (or chlorine atom) than the chlorinated alkane substrate, thechlorinated alkane substrate and the chlorinated alkane product having acarbon backbone structure that is in each case the same, the chlorinatedalkane product having a boiling point at least about 5° C. less than theat least one chlorinated carrier compound at about 1 atmospherepressure; (b) converting the pentavalent antimony catalyst to trivalentantimony catalyst to form a product comprising the at least onetrivalent antimony catalyst, the at least one chlorinated alkane productand the at least one chlorinated alkane carrier compound; (c) separatingat least a portion of the at least one chlorinated alkane product fromthe product comprising the at least one trivalent antimony catalyst, theat least one chlorinated alkane carrier compound, and any remainder ofthe at least one chlorinated alkane product by distillation; and (d)recycling the product comprising the at least one trivalent antimonycatalyst, the at least one chlorinated alkane carrier compound, and anyremainder of the at least one chlorinated alkane product to the reactionvessel of the chlorination process.

The features that characterize the present invention are pointed outwith particularity in the claims, which are annexed to and form a partof this disclosure. These and other features of the invention, itsoperating advantages and the specific objects obtained by its use willbe more fully understood from the following detailed description inwhich non-limiting embodiments of the invention are illustrated anddescribed.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is a schematic representation of a method of forming1,1,2,3-tetrachloropropene in accordance with some embodiments of thepresent invention;

FIG. 2 is a schematic representation of a method of forming1,1,2,3-tetrachloropropene in accordance with some further embodimentsof the present invention;

FIG. 3 is a schematic representation of a method of recycling at leastone polyvalent antimony catalyst from a product of a chlorinationprocess according to the present invention; and

FIG. 4 is a schematic representation of a method of recycling at leastone polyvalent antimony catalyst from a product of a chloroalkanedehydrochlorination process.

In FIGS. 1-4, like characters refer to the same equipment, streams,and/or components, such as conduits, reaction streams, reactors,condensers, and distillation columns, as the case may be, unlessotherwise stated.

DETAILED DESCRIPTION

As used herein, the singular articles “a,” “an,” and “the” includeplural referents unless otherwise expressly and unequivocally limited toone referent.

Unless otherwise indicated, all ranges or ratios disclosed herein are tobe understood to encompass any and all subranges or subratios subsumedtherein. For example, a stated range or ratio of “1 to 10” should beconsidered to include any and all subranges between (and inclusive of)the minimum value of 1 and the maximum value of 10; that is, allsubranges or subratios beginning with a minimum value of 1 or more andending with a maximum value of 10 or less, such as but not limited to, 1to 6.1, 3.5 to 7.8, and 5.5 to 10.

Other than in the operating examples, or where otherwise indicated, allnumbers expressing quantities of ingredients, reaction conditions, andso forth used in the specification and claims are to be understood asmodified in all instances by the term “about.”

All documents, such as but not limited to issued patents and patentapplications, referred to herein, and unless otherwise indicated, are tobe considered to be “incorporated by reference” in their entirety.

As used herein, the unit “psia” means pounds per square inch absolute,which is relative to vacuum.

As used herein, the unit “psig” means pounds per square inch gauge,which is relative to ambient atmospheric pressure.

As used herein, recitations of “alkyl” include “cycloalkyl” and/or“linear or branched alkyl.” Recitations of “linear or branched” groups,such as linear or branched alkyl, are herein understood to include: amethylene group or a methyl group; groups that are linear, such aslinear C₂-C₂₅ alkyl groups; and groups that are appropriately branched,such as branched C₃-C₂₅ alkyl groups.

The term “linear or branched alkyl” as used herein, in accordance withsome embodiments, means linear or branched C₁-C₂₅ alkyl, or linear orbranched C₁-C₁₀ alkyl, or linear or branched C₂-C₁₀ alkyl. Examples ofalkyl groups from which the various alkyl groups of the presentinvention can be selected from, include, but are not limited to, methyl,ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl,pentyl, neopentyl, hexyl, heptyl, octyl, nonyl and decyl.

The term “cycloalkyl” as used herein, in accordance with someembodiments, means alkyl groups that are appropriately cyclic, such asbut not limited to, C₃-C₁₂ cycloalkyl (including, but not limited to,C₅-C₇ cycloalkyl) groups. Examples of cycloalkyl groups include, but arenot limited to, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, andcyclooctyl. The term “cycloalkyl” as used herein in accordance with someembodiments also includes: bridged ring polycycloalkyl groups (orbridged ring polycyclic alkyl groups), such as but not limited to,bicyclo[2.2.1]heptyl (or norbornyl) and bicyclo[2.2.2]octyl; and fusedring polycycloalkyl groups (or fused ring polycyclic alkyl groups), suchas, but not limited to, octahydro-1H-indenyl, and decahydronaphthyl.

As used herein, recitations of “alkenyl” include “cycloalkenyl” and/or“linear or branched alkenyl” and means groups having at least oneethylenically unsaturated group, that are not aromatic. The term“alkenyl” as used herein, in accordance with some embodiments, includeslinear or branched C₂-C₂₅ alkenyl (including, but not limited to, linearor branched C₂-C₁₀ alkenyl). Examples of alkenyl groups include but arenot limited to vinyl, allyl, propenyl, butenyl, pentenyl, and hexenyl.The term “cycloalkenyl” as used herein, in accordance with someembodiments, means alkenyl groups that are appropriately cyclic, such asbut not limited to, C₃-C₁₂ cycloalkenyl (including, but not limited to,C₅-C₇ cycloalkenyl) groups. Examples of cycloalkenyl groups include, butare not limited to, cyclopropenyl, cyclobutenyl, cyclopentenyl,cyclohexenyl, cycloheptenyl, and cyclooctenyl.

As used herein, recitations of “alkynyl” include “cycloalkynyl” and/or“linear or branched alkynyl” and means groups having at least onecarbon-carbon triple bond. The term “alkynyl” as used herein, inaccordance with some embodiments, includes linear or branched C₂-C₂₅alkynyl (including, but not limited to, linear or branched C₂-C₁₀alkynyl). Examples of alkynyl groups include, but are not limited to,ethynyl, propynyl, butynyl (such as, 1-butynyl and 2-butynyl), pentynyl,hexynyl, heptynyl, and octynyl. The term “cycloalkynyl” as used herein,in accordance with some embodiments, means alkynyl groups that areappropriately cyclic, such as but not limited to, C₈-C₁₂ cycloalkynyl(including, but not limited to, C₈-C₁₀ cycloalkynyl) groups. Examples ofcycloalkynyl groups include, but are not limited to, cyclooctynyl, andcyclononynyl.

As used herein, the term “aryl” includes cyclic aryl groups andpolycyclic aryl groups. With some embodiments, aryl groups include, butare not limited to, C₆-C₁₈ aryl, such as C₆-C₁₀ aryl (includingpolycyclic aryl groups). Examples of aryl groups include, but are notlimited to, phenyl, naphthyl, anthracenyl and triptycenyl.

As used herein, the term “alkane” includes “cycloalkane” and/or “linearor branched alkane.” Recitations of “linear or branched alkane(s)” areherein understood to include: methane; alkanes that are linear, such aslinear C₂-C₂₅ alkanes; and alkanes that are appropriately branched, suchas branched C₃-C₂₅ alkanes.

The term “linear or branched alkane” as used herein, in accordance withsome embodiments, includes linear or branched C₁-C₂₅ alkane, or linearor branched C₁-C₁₀ alkane, or linear or branched C₂-C₁₀ alkane. Examplesof alkane groups from which the various alkanes of the present inventioncan be selected from, include, but are not limited to, methane, ethane,propane, isopropane, butane, isobutane, sec-butane, tert-butane,pentane, neopentane, hexane, heptane, octane, nonane and decane.

The term “cycloalkane” as used herein, in accordance with someembodiments, means alkanes that are appropriately cyclic, such as butnot limited to, C₃-C₁₂ cycloalkane (including, but not limited to, C₅-C₇cycloalkane). Examples of cycloalkane groups include, but are notlimited to, cyclopropane, cyclobutane, cyclopentane, cyclohexane,cycloheptane, and cyclooctane. The term “cycloalkane” as used herein inaccordance with some embodiments also includes: bridged ringpolycycloalkanes (or bridged ring polycyclic alkanes), such as but notlimited to, bicyclo[2.2.1]heptane (or norbornane) andbicyclo[2.2.2]octane; and fused ring polycycloalkanes (or fused ringpolycyclic alkanes), such as, but not limited to, octahydro-1H-indenane,and decahydronaphthalene.

As used herein, recitations of “alkene” include “cycloalkene” and/or“linear or branched alkene” and means alkanes having at least oneethylenically unsaturated group, that are not aromatic. The term “linearor branched alkene” as used herein, in accordance with some embodiments,means linear or branched C₂-C₂₅ alkene (including, but not limited to,linear or branched C₂-C₁₀ alkene). Examples of alkenes include, but arenot limited to, ethene, propene, butene, pentene, hexane, heptene,octane, nonene, and decene. The term “cycloalkene” as used herein, inaccordance with some embodiments, means alkenes that are appropriatelycyclic, such as but not limited to, C₃-C₁₂ cycloalkene (including, butnot limited to, C₅-C₇ cycloalkene). Examples of cycloalkenes include,but are not limited to, cyclopropene, cyclobutene, cyclopentene,cyclohexene, and cyclooctene.

As used herein, recitations of “alkyne” include “cycloalkyne” and/or“linear or branched alkyne” and means cycloalkanes or alkanes having atleast one carbon-carbon triple bond. The term “linear or branchedalkyne” as used herein, in accordance with some embodiments, meanslinear or branched C₂-C₂₅ alkyne (including, but not limited to, linearor branched C₂-C₁₀ alkyne). Examples of alkynes include, but are notlimited to, ethyne, propyne, butyne (such as, 1-butyne and 2-butyne),pentyne, hexyne, heptyne, and octyne. The term “cycloalkyne” as usedherein, in accordance with some embodiments, means alkyne groups thatare appropriately cyclic, such as but not limited to, C₈-C₁₂ cycloalkyne(including, but not limited to, C₈-C₁₀ cycloalkyne). Examples ofcycloalkynes include, but are not limited to, cyclooctyne andcyclononyne.

As used herein, the term “aromatic,” such as aromatic compound, includescyclic aromatic and polycyclic aromatic. With some embodiments, aromaticcompounds include, but are not limited to, C₆-C₁₈ aromatic compounds,such as C₆-C₁₀ aromatic compounds (including polycyclic aromaticcompounds). Examples of aromatic compounds include, but are not limitedto, benzene, naphthalene, anthracene and triptycene.

As used herein, the term “polyvalent antimony” and related terms, suchas “polyvalent antimony compound,” “polyvalent antimony catalyst,” and“polyvalent antimony catalyst compound” include, but are not limited to,pentavalent antimony, trivalent antimony, and combinations thereof.

The compound 1,1,1,2,3-pentachloropropane is inert to antimonypentachloride and antimony trichloride. Therefore,1,1,1,2,3-pentachloropropane can be used a process solvent for ionicchlorinations or cracking processes or added to a distillation processin which antimony trichloride preferentially stays with1,1,1,2,3-pentachloropropane so that lower-boiling components can beremoved from a crude mixture with little, if any, antimony content. Theantimony catalyst-enriched 1,1,1,2,3-pentachloropropane mixture can berecycled to allow considerable economic advantages byreducing/eliminating antimony waste disposal costs and additionalcatalyst purchase costs.

In accordance with some embodiments of the present invention, there isprovided a method of preparing 1,1,1,2,3-pentachloropropane thatinvolves reacting 1,1,1,3-tetrachloropropane with a source of chlorinein the presence of a polyvalent antimony compound that includes apentavalent antimony compound, thereby forming a product that includes1,1,1,2,3-pentachloropropane. The reaction, in some embodiments, isconducted in one or more suitable reactors. The method of preparing1,1,1,2,3-pentachloropropane is, in some embodiments, performed as abatch method, a continuous method, and combinations thereof, such ascombinations of one or more batch methods and one or more continuousmethods.

The 1,1,1,3-tetrachloropropane, in accordance with some embodiments, canbe obtained from any suitable source. With some embodiments, the1,1,1,3-tetrachloropropane is formed by reacting carbon tetrachloridewith ethylene in the presence of an iron chloride, iron metal, and atrialkylphosphate. Examples of iron chloride include, but are notlimited to, ferric chloride and/or ferrous chloride. The term “ironmetal” as used herein includes “metallic iron” and sources thereof.Examples of trialkylphosphates include, but are not limited to,triethylphosphates, tripropylphosphates and/or tributylphosphates.Preparation of 1,1,1,3-tetrachloropropane in accordance with suchmethods is described in, for example, U.S. Pat. Nos. 4,535,194,4,650,914, and 8,487,146 B2 (such as at column 4, line 20 through column5, line 55 thereof), and EP 0 131 561. Commercially available1,1,1,3-tetrachloropropane material can, with some embodiments, includechemical components derived from the chemical reactants used tosynthesize it. For example, commercially available1,1,1,3-tetrachloropropane can include contaminating levels of carbontetrachloride and other chlorinated hydrocarbons.

In accordance with some embodiments of the present invention, the1,1,1,3-tetrachloropropane used in the present process is substantiallyfree of chlorinated hydrocarbon contaminants, catalysts, other organicmaterials, such as alcohols with some embodiments, and is substantiallyfree of water, such as containing less than 1000 ppm by weight of waterwith some embodiments.

The method of preparing 1,1,1,2,3-pentachloropropane from1,1,1,3-tetrachloropropane in accordance with the present invention, isperformed in the presence of a source of chlorine. The source ofchlorine can be any source that provides chlorine for the reaction. Withsome embodiments, the source of chlorine does not have or cause anydeleterious consequences on the reaction, such as promoting orgenerating undesirable byproducts, poisoning the polyvalent antimonycatalyst, affecting the efficiency of the reaction, or affectingundesirably the temperature at which the chlorination reaction isconducted. The source of chlorine is liquid and/or gaseous chlorine(Cl₂), with some embodiments. In accordance with some embodiments, thesource of chlorine is selected from chlorine (Cl₂), sulfuryl chloride(SO₂Cl₂), and combinations thereof, such as combinations of chlorine(Cl₂) and sulfuryl chloride (SO₂Cl₂).

With some embodiments, the source of chlorine is chlorine (Cl₂), andreacting 1,1,1,3-tetrachloropropane with the source of chlorine isconducted with a mole ratio of chlorine (Cl₂) to1,1,1,3-tetrachloropropane of from 0.2:1 to 1.5:1, or from 0.2:1 to1.1:1, or from 0.9:1 to 1.1:1, such as 1:1 (inclusive of the recitedvalues).

In some instances, if an excessive amount of chlorine is used, such asgreater than 1.5:1 (ratio of chlorine (Cl₂) to1,1,1,3-tetrachloropropane), other pentachloropropanes, such as1,1,1,3,3-pentachloropropane and over-chlorinated materials, can, withsome embodiments, be produced as byproducts. Conversely, if the amountof chlorine used is significantly lower than 0.2:1 (ratio of chlorine(Cl₂) to 1,1,1,3-tetrachloropropane), an increased amount of unreactedmaterial can, with some embodiments, result, which requires removalthereof from the reactor (such as by distillation), and disposal orreuse thereof, which can lead to higher capital and operating costs.

The method of preparing 1,1,1,2,3-pentachloropropane from1,1,1,3-tetrachloropropane in accordance with the present invention, isperformed in the presence of a polyvalent antimony compound, whichincludes a pentavalent antimony compound. With some embodiments, thepolyvalent antimony compound(s) include(s) the pentavalent antimonycompound(s) and optionally a trivalent antimony compound(s).

The pentavalent antimony compound, with some embodiments, includes oneor more pentavalent antimony compounds represented by the followingFormula (I),Sb(R¹)_(a)(Cl)_(b)  (I)With reference to Formula (I), the sum of a and b is 5, provided that bis at least 2, and R¹ independently for each a is selected from linearor branched alkyl, cyclic alkyl, and/or aryl.

With further reference to Formula (I), classes and examples of thelinear or branched alkyl groups, cyclic alkyl groups, and aryl groupsfrom which R¹ can be independently selected for each subscript ainclude, but are not limited to those classes and examples as recitedpreviously herein, such as linear or branched C₁-C₂₅ alkyl groups,C₃-C₁₂ cycloalkyls, and/or C₆-C₁₈ aryl, and related examples thereof.

Examples of pentavalent antimony compounds that can be used with someembodiments of the present invention include, but are not limited to:antimony pentachloride; trialkyl antimony dichloride, such as tributylantimony dichloride; and triaryl antimony dichloride, such as triphenylantimony dichloride.

The trivalent antimony compound, includes, with some embodiments, one ormore trivalent antimony compounds represented by the following Formula(II),Sb(R²)_(c)(Cl)_(d)  (II)With reference to Formula (II), c is from 0 to 3, d is from 0 to 3,provided that the sum of c and d is 3, and R² independently for each cis selected from linear or branched alkyl, cyclic alkyl, and/or aryl.

With further reference to Formula (II), classes and examples of thelinear or branched alkyl groups, cyclic alkyl groups, and aryl groupsfrom which R² can be independently selected for each subscript cinclude, but are not limited to those classes and examples as recitedpreviously herein, such as, C₁-C₂₅ alkyl groups, C₃-C₁₂ cycloalkyls,and/or C₆-C₁₈ aryl, and related examples thereof.

Examples of trivalent antimony compounds that can be used with someembodiments of the present invention include, but are not limited to:antimony trichloride, trialkyl antimony, such as tributyl antimony; andtriaryl antimony, such as triphenyl antimony.

In accordance with some embodiments, the method of preparing1,1,1,2,3-pentachloropropane includes forming at least a portion of thepentavalent antimony compound from a precursor of the pentavalentantimony compound. In accordance with some further embodiments, theprecursor of the pentavalent antimony compound includes one or moretrivalent antimony compounds represented by Formula (II) above. Withsome embodiments, the precursor of the pentavalent antimony compound iscontacted with the source of chlorine, such as chlorine (Cl₂), such asin a reaction zone of a reactor, and at least a portion of the precursorof the pentavalent antimony compound is converted to a pentavalentantimony compound. For purposes of nonlimiting illustration, contactbetween antimony trichloride (as a precursor compound) and a source ofchlorine, such as chlorine (Cl₂) results in conversion of at least aportion of the antimony trichloride to antimony pentachloride. Inaccordance with some embodiments, the method of the present invention isperformed in the presence of both one or more pentavalent antimonycompounds and one or more trivalent antimony compounds.

The precursor of the pentavalent antimony compound, with someembodiments, is selected from antimony trichloride, trialkyl antimony,triaryl antimony, and combinations of two or more thereof. With someadditional embodiments, the precursor of the pentavalent antimonycompound, is selected from antimony trichloride, triphenyl antimony, andcombinations thereof.

The amount of polyvalent antimony compound used for the reaction thatresults in the formation of 1,1,1,2,3-pentachloropropane can, with someembodiments, vary widely. With some embodiments, the polyvalent antimonycompound is present in an amount that is effective to catalyze thedescribed reaction, such as being present in a catalytic amount. If morethan an effective amount of polyvalent antimony compound is used, thecost of the polyvalent antimony compound itself and/or the disposalcosts associated with used (or spent) polyvalent antimony compound canbe taken into account, as such costs can affect (such as increase) theoverall cost of the process, with some embodiments.

The effective amount of polyvalent antimony catalyst used can alsodepend on the other reaction conditions used, such as temperature,pressure, reactant flow rates, type of reaction vessel, etc. In the caseof antimony pentachloride, which is a liquid at standard (or ambient)conditions, the amount of pentavalent antimony catalyst used for theliquid chlorination reaction can vary, with some embodiments, from 0.05to 2 volume percent, based on the volume of the1,1,1,3-tetrachloropropane reactant, such as 0.5 volume percent. Withsome embodiments, the amount of pentavalent antimony catalyst used canvary from 0.05 to 0.5 volume percent. A larger amount of pentavalentantimony catalyst in the reaction results in a reduced amount of time tocomplete the reaction, with some embodiments, compared to smalleramounts of pentavalent antimony catalyst.

In accordance with some embodiments of the present invention: (i) thepolyvalent antimony compound is used in a free form, such as free ofbeing supported on a solid support; and/or (ii) the polyvalent antimonycompound is supported on a solid support (or solid carrier), such as asolid particulate support. With some further embodiments, the polyvalentantimony compound is supported on a solid support (or solid carrier),such as a solid particulate support. The solid support, with someembodiments, is selected from one or more silica supports, one or morealumina supports, one or more zeolite supports, one or more claysupports, one or more activated carbon supports, and combinations of twoor more thereof.

Amorphous silica, such as precipitated silica can be used to support thepolyvalent antimony compound (and/or a precursor material thereof), withsome embodiments. The size of the amorphous silica powder can vary, andfalls within a size range of from 60 to 200 mesh (U.S. screen size),with some embodiments. Any of the crystalline forms of silica can beused as a support, with some embodiments. With some embodiments, silicain one or more of the following crystalline forms is used: quartz;tridymite; and cristobalite.

Zeolites that can be used to support the polyvalent antimony compound(and/or a precursor material thereof) include, but are not limited to,the synthetic or naturally occurring aluminum and calcium, or aluminumand sodium silicates that are suitable for use in chlorinationreactions. Such zeolites include, with some embodiments, those of thegeneral type Na₂O.2Al₂O₃.5SiO₂ and CaO.2Al₂O₃.5SiO₂. Aluminas that canbe used as a support for the polyvalent antimony compound (and/or aprecursor material thereof) include those that are solid and suitablefor use in chlorination reactions. Examples of such materials includethe various crystalline forms of alumina, activated alumina, andcalcined aluminas, which include the stable form of anhydrous alumina(α-Al₂O₃). The particle size of the solid support can be in the rangedescribed for the amorphous precipitated silica, with some embodiments.The polyvalent antimony compound is chemically bonded to the supportsurface rather than simply deposited on the surface, with someembodiments, which can result in a reduction in the amount of polyvalentantimony compound lost during the chlorination reaction.

The supported polyvalent antimony compound can be prepared by techniquesknown to those skilled in the art, with some embodiments. For purposesof non-limiting illustration, antimony trichloride can be dissolved intoluene and refluxed overnight in the presence of the solid catalystsupport, such as amorphous silica. Subsequently, the silica is cooled,separated from the liquid toluene, such as by filtration or some othersuitable liquid-solid separation methods, washed with a solvent, such astoluene or absolute ethanol, and dried. While not intending to be boundby any theory, it is believed, with some embodiments, that at least someof the trivalent antimony supported on the solid support is converted inthe presence of a source of chlorine, such as chlorine (Cl₂), topentavalent antimony, which is also supported on the solid support.

In accordance with some embodiments of the present invention, reacting1,1,1,3-tetrachloropropane with the source of chlorine in the presenceof the polyvalent antimony compound is conducted at a temperature of atleast 40° C. The temperature of the reactions, such as in the reactionzone, can range from 40° C. to 200° C., or from 50° C. to 120° C., orfrom 80° C. to 120° C., with some embodiments. A higher temperaturewithin a described range, such as in the reaction zone, results in afaster chlorination reaction, but increased co-production of undesirablebyproducts, such as hexachloropropanes, undesired pentachloropropanes,and materials generally referred to as heavies or bottom products, withsome embodiments. As such, and with some embodiments, the production of1,1,1,2,3-pentachloropropane is performed at a temperature range of 40°C. to 200° C., which can provide a desirable rate of reaction andminimize the number and amount of byproducts formed, with someembodiments.

The pressure (such as within the reaction zone) for the reaction of1,1,1,3-tetrachloropropane with a source of chlorine in the presence ofa polyvalent antimony compound so as to form1,1,1,2,3-pentachloropropane, can vary, with some embodiments of thepresent invention. With some embodiments, the pressure is at least 1psia. With some further embodiments, the pressure is from 1 psia to 500psia, such as from 1 psia to 200 psia. Operation at high pressures, suchas at least 100 psia, makes recovery of the hydrogen chloride (HCl)co-product easier, with some embodiments. Subatmospheric pressures canbe used with some embodiments of the present invention. With somefurther embodiments, subatmospheric pressures are avoided.

In accordance with some embodiments of the present invention, reacting1,1,1,3-tetrachloropropane with the source of chlorine in the presenceof the polyvalent antimony compound, so as to form1,1,1,2,3-pentachloropropane, is conducted at a temperature of at least40° C., and a pressure of at least 1 psia.

In accordance with some further embodiments of the present invention,reacting 1,1,1,3-tetrachloropropane with the source of chlorine in thepresence of the polyvalent antimony compound, so as to form1,1,1,2,3-pentachloropropane, is conducted at a temperature of from 40°C. to 200° C., and a pressure is from 1 psia to 500 psia. With someembodiments, the chlorination methods of the present invention provideimproved product selectivity and reduced byproduct production, comparedto previous chlorination methods, such as those which are performed inthe presence of ferric chloride or aluminum chloride.

Reacting 1,1,1,3-tetrachloropropane with a source of chlorine in thepresence of the polyvalent antimony compound, so as to form1,1,1,2,3-pentachloropropane, is conducted in the liquid phase and undersubstantially dry conditions, with some embodiments, because thepresence of water, such as within the reaction zone, can result ineither deactivation of the polyvalent antimony compound and/or thegeneration of hypochlorous acid (HOCl) from the reaction of chlorinewith water, which can result in the generation of undesirable oxygenatedby-products. While not intending to be bound by any theory, it isthought that the presence of water, such as in the reaction zone, cancause the production of hydrochloric acid, because of the reaction ofwater with chlorine and/or the hydrogen chloride co-product.Hydrochloric acid is an undesirable by-product, which can causecorrosion of vessels, piping, pumps and other equipment that wouldrequire the use of equipment made of more expensive hydrochloric acidresistant materials, with some embodiments. In accordance with someembodiments, the reactants, catalyst, etc. charged to the reactor (suchas to the reaction zone) have less than 0.1 weight percent water, andwhich can be described as being substantially dry with some embodiments.The reactants and the reaction medium can contain less than 1000 ppm ofwater, such as from 5 to 1000 ppm of water, with some embodiments. Waterthat is present in the reactor before beginning the process (or waterthat enters the reactor subsequently, such as due to processinterruptions) can be expunged by purging the reactor with asubstantially dry or dried gas, such as dry nitrogen, hydrogen chloride,or chlorine.

The reaction time, for the reaction of 1,1,1,3-tetrachloropropane with asource of chlorine in the presence of the polyvalent antimony compound,so as to form 1,1,1,2,3-pentachloropropane, in accordance with someembodiments of the present invention can vary, and can depend on variousparameters, such as the temperature at which the reaction is performed,the amount of antimony catalyst used, the nature of the reaction vessel,the desired degree of conversion of the 1,1,1,3-tetrachloropropanereactant, the chlorine feed rate, etc. According to some embodiments,the reaction time can vary from 0.5 to 12 hours, or from 3 to 5 hours,when the reaction is performed in a batch mode. Too long of a reactiontime, due to for example restricting chlorine flow to the reactor, canresult in an increased formation of undesirable dimerization byproducts,with some embodiments.

When performed in a continuous mode, the flow of reactants into thereactor, the reaction temperature (and pressure), and the volumetricflow of effluents withdrawn from the reactor are chosen to also achievethe desired degree of conversion of the 1,1,1,3-tetrachloropropanereactant to 1,1,1,2,3-pentachloropropane, while minimizing byproductformation, in accordance with some embodiments. When conducted in acontinuous mode, the average residence time in the reactor can vary from0.5 to 12 hours, or from 3 to 5 hours, with some embodiments. Theaverage residence time is defined as the reactor volume divided by theflow rate of 1,1,1,3-tetrachloropropane reactant into the reactor, withsome embodiments.

With some embodiments, the reaction of 1,1,1,3-tetrachloropropane with asource of chlorine in the presence of the polyvalent antimony compound,so as to form 1,1,1,2,3-pentachloropropane is performed in a reactorthat is fabricated from materials resistant to corrosion by the reactantmaterials, such as chlorine, the reaction mixture and the products,co-products and byproducts resulting from the reaction, such as hydrogenchloride and 1,1,1,2,3-pentachloropropane. Suitable materials from whichthe reactor can be constructed with some embodiments include, but arenot limited to, glass, such as glass-lined steel vessels, nickel, nickelalloys, tantalum, fluorohydrocarbon polymers, such as HALAR-lined orTEFLON-lined vessels, such as polytetrafluoroethylene-lined vessels. Thereactor vessel itself can be of any suitable design for chlorinationreactions of the type described. With some embodiments, the reactor canbe a vertical cylindrical vessel, or tubular in design, the design ofwhich can accommodate the temperatures, pressures and corrosiveenvironment associated with the chlorination process. The reactor can bepacked with the supported catalyst, as in the case of a plug flowtubular reactor, or operated like a continuously stirred tank reactor,with some embodiments. If the catalyst is not supported by a solidcarrier, but remains in liquid form, such as antimony pentachloride, orsolid form, the reactor can have agitation means, such as agitators, toobtain intimate contact between the source of chlorine,1,1,1,3-tetrachloropropane, and the polyvalent antimony compound, and toprovide adequate contact of the reaction mixture with heat-transfersurfaces so as to enable adequate temperature control, with someembodiments.

The reaction of 1,1,1,3-tetrachloropropane with a source of chlorine inthe presence of the polyvalent antimony compound, so as to form1,1,1,2,3-pentachloropropane can be performed as a batch and/orcontinuous reaction, with some embodiments. In both modes, the reactoris associated with additional equipment, such as heating means to bringthe reaction mixture to the desired reaction temperature, cooling meansto remove exothermic heat from the reaction zone, such as by the coolingof the 1,1,1,3-tetrachloropropane reactant or by cooling coils withinthe reactor, heat exchanger means to control the temperature of gasesand effluents removed from the reactor where required, gaseous effluentscrubbers, solid-liquid separators, and distillation columns to handlehydrogen chloride co-product off-gas, the separation of the principalproduct from any byproducts, and the separation of polyvalent antimonycompound(s) withdrawn along with liquid heavy by-products.

In accordance with some embodiments, the reactants1,1,1,3-tetrachloropropane and gaseous chlorine are introducedcontinuously into a cylindrical glass-lined reactor equipped with anagitator and containing 1,1,1,3-tetrachloropropane as the liquidreaction medium and polyvalent antimony compound. The temperature of theliquid reaction medium is controlled, such as cooled, by means of heatexchange coils in or around the reaction zone.

Hydrogen chloride co-product effluent (which can be in the form of agaseous hydrogen chloride co-product effluent) is removed from thereactor overhead and separated, if necessary, from any chlorinatedhydrocarbons carried with it, with some embodiments. The resultantrecovered hydrogen chloride is substantially anhydrous and can either:(a) be further purified and used (or sold for use) in otherapplications; (b) dissolved in water and sold as hydrochloric acid; or(c) scrubbed with an alkali, such as sodium hydroxide, to neutralize thehydrogen chloride, with some embodiments. The resultant alkali metalchloride salt, such as sodium chloride, from such neutralization can bedisposed of in an environmentally accepted manner or, in the case ofsodium chloride, used as feedstock to a chlorine-caustic electrolyticcell circuit, with some further embodiments.

A crude product stream effluent that includes1,1,1,2,3-pentachloropropane is removed from the reactor and optionallyforwarded to a distillation zone containing one or more distillationcolumns (depending on the composition of the product stream and thedesign of the distillation column), with some embodiments. Polyvalentantimony compounds (such as, pentavalent antimony compounds and/ortrivalent antimony compounds) and unreacted 1,1,1,3-tetrachloropropaneseparated from this crude product stream in a distillation zone can berecycled back to the reactor (where the reaction of1,1,1,3-tetrachloropropane with a source of chlorine in the presence ofthe polyvalent antimony compound, so as to form1,1,1,2,3-pentachloropropane, is conducted). Chlorine is optionallyadded to the distillation zone to maintain or increase the fraction ofpolyvalent antimony compound in the pentavalent state, which enhancesthe recovery of pentavalent antimony compound, in accordance with someembodiments of the present invention. If necessary, the1,1,1,2,3-pentachloropropane product can be further purified in one ormore additional distillation zones containing one or more distillationcolumns. Byproducts from the distillation zone(s) are recycled to theprocess or disposed of in an environmentally acceptable way, with someembodiments.

In some embodiments, there is provided a technique for recoveringantimony trichloride or antimony pentachloride for use as a catalyst inthe chlorination of hydrocarbons or the cracking of halohydrocarbons bythe use of a carrier compound having a boiling point close to antimonytrichloride and higher than that of the reaction product. The antimonycatalyst-enriched mixture can be recycled to allow considerable economicadvantages by reducing/eliminating antimony waste disposal costs andadditional catalyst purchase costs.

In some embodiments, a method for separating a portion of at least onechlorinated alkane product from a product comprising at least onepentavalent antimony catalyst (discussed above), at least onechlorinated alkane carrier compound, and at least one chlorinated alkaneproduct is provided. The method comprises providing a product comprisingat least one pentavalent antimony catalyst, at least one chlorinatedalkane carrier compound having a boiling point between about 170° C. andabout 250° C. at about 1 atmosphere pressure, and at least onechlorinated alkane product having a boiling point at least about 5° C.less than the at least one chlorinated carrier compound at about 1atmosphere pressure, and converting the pentavalent antimony catalyst totrivalent antimony catalyst to form a product comprising at least onetrivalent antimony catalyst, at least one chlorinated alkane carriercompound, and at least one chlorinated alkane product. The methodcomprises separating at least a portion of the at least one chlorinatedalkane product from the product comprising the at least one trivalentantimony catalyst, the at least one chlorinated alkane carrier compound,and any remainder of the at least one chlorinated alkane product bydistillation, as shown in FIG. 3.

The chlorinated alkane product can be any of the chlorinated alkanesubstrates discussed herein having a boiling point at least about 5° C.less than the at least one chlorinated carrier compound at about 1atmosphere pressure. Non-limiting examples of suitable chlorinatedalkane products or substrates include 1,1,1,2,3-pentachloropropane,1,1,2-trichloropropane, and 1,1,1,2-tetrachloropropane. Suitablepentavalent antimony catalysts or compounds are discussed herein.Suitable chlorinated alkane carrier compounds having a boiling pointbetween about 170° C. and about 250° C. at about 1 atmosphere pressure,and can include, for example, chlorinated alkanes which do not reactwith the pentavalent antimony catalyst and chlorine to form undesirableside products, e.g., a polychlorinated alkane such as1,1,1,2,2-pentachloroethane or 1,1,1,2,3-pentachloropropane (b.p. 196°C.), which is a suitable carrier compound because it has a boiling pointclose to antimony trichloride (b.p. 220.3° C.) and antimony trichlorideis readily soluble in it. Other C₂-C₅ chloroalkanes that would also besuitable include hexachloroethane (b.p. 187° C.),1,1,2,3,3-pentachloropropane (b.p. 198° C.), and1,1,1,2,2,3-hexachlorobutane (b.p. 218° C.). Compounds with a boilingpoint between 170° C. and 250° C. will stay with antimony trichloride inthe distillation column bottoms, allowing for removal of thelower-boiling product from the top of the distillation column.

Lower-boiling distillation products may include 1,1,2-trichloropropane,and 1,1,1,2-tetrachloropropane. Reaction products having a boiling pointlower than the C₂-C₅ chloroalkane will be suitable to complete theseparation. It is preferred that the boiling point of the carriercompound be at least 5° C. greater than the boiling point of thereaction product. More preferred is the boiling point of the carriercompound being at least 10° C. greater than the boiling point of thereaction product.

In order to separate the antimony chlorides from the reaction product,the antimony must be substantially in the form of antimony trichloride.If the reaction product contains antimony pentachloride, it must firstbe converted to antimony trichloride by suitable methods known to theart. These methods include heating while sparging with an inert gas orreduction with a reducing agent such as hydrogen.

The distillation bottoms comprising the C₂-C₅ chloroalkane and antimonytrichloride can then be recycled to the reactor for re-use as a catalystin the chlorination of hydrocarbons and/or the cracking ofhalohydrocarbons.

The distillation can occur at pressures between 1 torr and 100 psig,although lower pressures are preferred as they do not require heatingthe compounds to as high a temperature. Pressures between 100 torr and1000 torr are preferred.

If necessary, the antimony trichloride contained in the C₂-C₅chloroalkane can be converted to antimony pentachloride by the additionof chlorinating agent such chlorine gas prior to its use as a catalystin the chlorination of hydrocarbons and/or the cracking ofhalohydrocarbons.

In some embodiments, a method of recycling at least one polyvalentantimony catalyst from a product of a chlorination process is provided,the method comprising: (a) providing a product comprising at least onepentavalent antimony catalyst, at least one chlorinated alkane carriercompound having a boiling point between about 170° C. and about 250° C.at about 1 atmosphere pressure, and at least one chlorinated alkaneproduct having a boiling point at least about 5° C. less than the atleast one chlorinated carrier compound at about 1 atmosphere pressure;(b) converting the pentavalent antimony catalyst to trivalent antimonycatalyst to form a product comprising at least one trivalent antimonycatalyst, at least one chlorinated alkane carrier compound, and at leastone chlorinated alkane product; (c) separating at least a portion of theat least one chlorinated alkane product from the product comprising theat least one trivalent antimony catalyst, the at least one chlorinatedalkane carrier compound, and any remainder of the at least onechlorinated alkane product by distillation; and (d) recycling theproduct comprising the at least one trivalent antimony catalyst, the atleast one chlorinated alkane carrier compound, and any remainder of theat least one chlorinated alkane product to a chlorination process, asdiscussed herein.

In some embodiments, a method of further chlorinating at least onechlorinated alkane substrate, comprising: (a) reacting in a reactionvessel at least one chlorinated alkane substrate with a source ofchlorine in the presence of at least one pentavalent antimony catalystand at least one chlorinated alkane carrier compound having a boilingpoint between about 170° C. and about 250° C. at about 1 atmospherepressure, thereby forming a product comprising at least one chlorinatedalkane product, the at least one chlorinated alkane carrier compound,and the at least one pentavalent antimony catalyst, the chlorinatedalkane product having covalently bonded thereto at least one more chlorogroup (or chlorine atom) than the chlorinated alkane substrate, thechlorinated alkane substrate and the chlorinated alkane product having acarbon backbone structure that is in each case the same, the chlorinatedalkane product having a boiling point at least about 5° C. less than theat least one chlorinated carrier compound at about 1 atmospherepressure; (b) converting the pentavalent antimony catalyst to trivalentantimony catalyst to form a product comprising the at least onetrivalent antimony catalyst, the at least one chlorinated alkane productand the at least one chlorinated alkane carrier compound; (c) separatingat least a portion of the at least one chlorinated alkane product fromthe product comprising the at least one trivalent antimony catalyst, theat least one chlorinated alkane carrier compound, and any remainder ofthe at least one chlorinated alkane product by distillation; and (d)recycling the product comprising the at least one trivalent antimonycatalyst, the at least one chlorinated alkane carrier compound, and anyremainder of the at least one chlorinated alkane product to the reactionvessel of the chlorination process.

In accordance with some further embodiments of the present invention,there is provided a method of forming an alkene product. The method offorming the alkene product includes, with some embodiments, heating achlorinated alkane substrate in the presence of ferric chloride and apolyvalent antimony compound comprising a pentavalent antimony compound,thereby forming a product comprising the alkene product. The alkeneproduct optionally has at least one chlorine group covalently bondedthereto, and the chlorinated alkane substrate and the alkene producteach have a carbon backbone structure that is in each case the same.This reaction can be referred to herein as a dehydrochlorination orcracking reaction. The terms dehydrochlorination or cracking (or termsof like import), as used herein, are used interchangeably to refer tothe chemical rearrangement within a chlorinated alkane substrate thatresults in the creation of a double bond typically via the mechanism ofthe removal of a hydrogen atom and a chlorine atom from adjacent carbonatoms. The dehydrochlorination step is performed as a liquid phasereaction, with some embodiments.

During formation of the alkene product from the chlorinated alkanesubstrate, the carbon backbone of the chlorinated alkane substrate isnot modified, and the carbon atoms of the chlorinated alkane substrateare not rearranged. As such, the chlorinated alkane substrate and thealkene product each have a carbon backbone structure that is in eachcase the same. For purposes of non-limiting illustration, when thechlorinated alkane substrate is a chlorinated propane, the correspondingalkene product is an optionally chlorinated propene. With someembodiments, the chlorinated alkane substrate has no carbon-carbondouble bonds, and the alkene product has a single carbon-carbon doublebond.

The alkene product is, with some embodiments, selected from thoseclasses and examples of alkenes as described previously herein, whichcan further have at least one chlorine group (or atom) covalently bondedthereto. With some embodiments, the alkene product has one less chlorineatom covalently bonded thereto than the chlorinated alkane substrate.With some embodiments, the alkene product has one less chlorine atomcovalently bonded thereto and one less hydrogen atom bonded thereto,compared to the chlorinated alkane substrate. For purposes ofnonlimiting illustration, when the chlorinated alkane substrate is apentachloropropane, the corresponding alkene product is atetrachloropropene, with some embodiments. With some furtherembodiments: (i) the alkene product has one less chlorine atomcovalently bonded thereto than the chlorinated alkane substrate; (ii)the alkene product has one less hydrogen atom covalently bonded theretothan the chlorinated alkane substrate; (iii) the alkene product has asingle carbon-carbon double bond; and (iv) the chlorinated alkanesubstrate has no (or is free of) carbon-carbon double bonds. Examples ofoptionally chlorinated alkene products include, but are not limited to:optionally chlorinated linear or branched C₂-C₂₅ alkenes, such asoptionally chlorinated linear or branched C₂-C₁₀ alkenes, or optionallychlorinated linear or branched C₂-C₆ alkenes; and optionally chlorinatedC₃-C₁₂ cycloalkenes, such as optionally chlorinated C₅-C₇ cycloalkenes.Further examples of optionally chlorinated linear or branched alkeneproducts include, but are not limited to, ethene, propene, butene,pentene, hexene, heptene, octene, nonene, and decene, which in each caseoptionally and independently include at least one chlorine group (oratom) bonded thereto. Further examples of optionally chlorinatedcycloalkene products include, but are not limited to, cyclopropene,cyclobutene, cyclopentene, cyclohexene, cycloheptene, and cyclooctene,which in each case optionally and independently include at least onechlorine group (or atom) bonded thereto. Additional examples of alkeneproducts include, but are not limited to, 1,1,2,3-tetrachloropropene,1,2,3,3-tetrachloropropene, and 1,1,2,3,3-pentachloropropene.

The chlorinated alkane substrate (from which the alkene product isformed), with some embodiments, is selected from those classes andexamples of alkanes as described previously herein, which further haveat least one chlorine group (or atom) covalently bonded thereto. Withsome embodiments, the chlorinated alkane substrate is selected fromthose classes and examples of alkanes described previously herein, inwhich (i) at least one hydrogen thereof, and (ii) up to less than all ofthe hydrogens thereof are replaced with chlorine groups (or atoms)bonded to the carbon backbone structure thereof. With some furtherembodiments, the chlorinated alkane substrate is selected from thoseclasses and examples of alkanes described previously herein, in which(i) at least one hydrogen thereof, and (ii) up to all of the hydrogensthereof are replaced with chlorine groups (or atoms) bonded to thecarbon backbone structure thereof. Examples of chlorinated linear orbranched alkane substrates include, but are not limited to, chlorinatedlinear or branched C₂-C₂₅ alkanes, or chlorinated linear or branchedC₂-C₁₀ alkanes, or chlorinated linear or branched C₂-C₁₀ alkanes, orchlorinated linear or branched C₂-C₆ alkanes, which in each caseindependently have bonded thereto at least one chlorine group (or atom).Examples of chlorinated cycloalkane substrates include, but are notlimited to, chlorinated C₃-C₁₂ cycloalkanes or chlorinated C₅-C₇cycloalkanes, which each independently have bonded thereto at least onechlorine group (or atom). Further examples of chlorinated linear orbranched alkane substrates include, but are not limited to, ethane,propane, isopropane, butane, isobutane, sec-butane, tert-butane,pentane, neopentane, hexane, heptane, octane, nonane, and decane, whichin each case independently have bonded thereto at least one chlorinegroup (or atom). Further examples of chlorinated cycloalkane substratesinclude, but are not limited to, cyclopropane, cyclobutane,cyclopentane, cyclohexane, cycloheptane, and cyclooctane, which in eachcase independently have bonded thereto at least one chlorine group (oratom). Additional examples of chlorinated alkane substrates include, butare not limited to: 1,1,1,2,3-pentachloropropane;1,1,2,3,3-pentachloropropane; and 1,1,1,2,3,3-hexachloropropane.

In accordance with some embodiments, the chlorinated alkane substrate is1,1,1,2,3-pentachloropropane, and the alkene product is1,1,2,3-tetrachloropropene.

With some embodiments, the polyvalent antimony compound, that is used inthe formation of the alkene product, includes a pentavalent antimonycompound and optionally a trivalent antimony compound. The pentavalentantimony compound can, with some embodiments, include one or morepentavalent antimony compounds represented by Formula (I), as describedpreviously herein. The trivalent antimony compound can, with someembodiments, include one or more trivalent antimony compoundsrepresented by Formula (II), as described previously herein.

The polyvalent antimony compound, that is used in the formation of thealkene product, includes, with some embodiments, both: (i) a pentavalentantimony compound, which includes antimony pentachloride; and (ii) atrivalent antimony compound, which includes antimony trichloride.

The alkene product and hydrogen chloride co-product are withdrawn fromthe dehydrochlorination reaction zone, and each purified, and recovered,with some embodiments. It has been observed that use of the describedmixture of ferric chloride and polyvalent antimony compound reducessignificantly the dehydrochlorination reaction time, compared to, usingonly ferric chloride as the dehydrochlorination catalyst. Further, theonset of significant conversion of chlorinated alkane substrate toalkene product occurs at temperatures that are 30° to 60° C. below thetemperatures at which significant conversion occurs when using ferricchloride alone to catalyze the dehydrochlorination reaction, with someembodiments.

With some embodiments, ferric chloride and the polyvalent antimonycompound are each independently present in a catalytic amount, duringformation of the alkene product (or during the dehydrochlorinationreaction). With some embodiments, the polyvalent antimony compound ispresent in an amount of from 0.01 percent by weight to 10 percent byweight, or from 0.1 percent by weight to 2 percent by weight, in eachcase based on weight of 1,1,1,2,3-pentachloropropane; and the ferricchloride is present in an amount of from 0.01 percent by weight to 10percent by weight, or from 0.1 percent by weight to 5 percent by weight,in each case based on weight of 1,1,1,2,3-pentachloropropane.

In accordance with some embodiments of the present invention, thedehydrochlorination of the chlorinated alkane substrate is conducted inthe liquid phase. With some further embodiments, when the chlorinatedalkane substrate is 1,1,1,2,3-pentachloropropane and the alkene productis 1,1,2,3-tetrachloropropene, the dehydrochlorination of1,1,1,2,3-pentachloropropane (so as to form 1,1,2,3-tetrachloropropene),is performed at temperatures of from 50° C. to 200° C., or from 100° C.to 165° C.

With some embodiments, the dehydrochlorination reaction is conducted ata pressure of at least 0.6 psia. With some further embodiments, thedehydrochlorination reaction is conducted at a pressure of from 0.6 psiato 215 psia, or from 1 psia to 115 psia. Use of relatively highpressures, such as at least 100 psia, allows the hydrogen chlorideco-product to be recovered more easily. With some embodiments,subatmospheric dehydrochlorination reaction pressures are used (such asat least 0.6 psia). With some further embodiments, subatmosphericdehydrochlorination reaction pressures are avoided. With someembodiments, while not intending to be bound by any theory, and based onthe evidence presently at hand, the pressure under-which thedehydrochlorination reaction is conducted, is not believed to materiallyaffect the dehydrochlorination of the chlorinated alkane substrate, suchas 1,1,1,2,3-pentachloropropane.

The weight ratio of ferric chloride to polyvalent antimony compound inthe catalyst mixture used in the dehydrochlorination reaction can vary,with some embodiments of the present invention, such as from 1000:1 to1:1000 {FeCl₃:polyvalent antimony compound}, such as from 1000:1 to1:1000 {FeCl₃:(pentavalent antimony compound and optionally trivalentantimony compound)}, such as from 1000:1 to 1:1000 {FeCl₃:(antimonypentachloride and optionally antimony trichloride)}.

When the chlorinated alkane substrate is 1,1,1,2,3-pentachloropropaneand the alkene product is 1,1,2,3-tetrachloropropene, heating1,1,1,2,3-pentachloropropane in the presence of ferric chloride and thepolyvalent antimony compound (so as to form 1,1,2,3-tetrachloropropene)is conducted at: temperatures of from 50° C. to 200° C., or from 100° C.to 165° C.; and a pressure of from 0.6 psia to 215 psia, or from 0.6psia to 115 psia, with some embodiments.

When the chlorinated alkane substrate is 1,1,1,2,3-pentachloropropaneand the alkene product is 1,1,2,3-tetrachloropropene, heating1,1,1,2,3-pentachloropropane in the presence of ferric chloride and thepolyvalent antimony compound (so as to form 1,1,2,3-tetrachloropropene)is conducted with a mole ratio of ferric chloride to polyvalent antimonycompound of from 1000:1 to 1:1000.

Any reactor that is of suitable design to accommodate thedehydrochlorination reaction and the temperature, pressure and corrosiveenvironment of the reactant materials, polyvalent antimony compound(s),ferric chloride, the reaction mixture, and the products, co-products andbyproducts resulting from the reaction, such as hydrogen chloride and1,1,2,3-tetrachloropropene, can be used to perform thedehydrochlorination of the chlorinated alkane substrate so as to formthe corresponding alkene product. Examples of suitable reactor designsinclude vertical cylindrical vessels or tubular, such as plug-flow,reactors fabricated from appropriate materials of construction, such ascorrosion resistant materials. Suitable materials of constructioninclude carbon steel, glass, such as glass-lined steel vessels, nickel,nickel alloys, tantalum, fluorohydrocarbon polymers, such as,HALAR-lined or TEFLON-lined vessels, such aspolytetrafluoroethylene-lined vessels.

The dehydrochlorination reactor can have one or more agitators forcontinuous agitation (or stirring) of the reaction medium in order toobtain intimate and adequate contact between the chlorinated alkanesubstrate and the polyvalent antimony compound(s) and ferric chloride,and to provide adequate contact of the reaction mixture with heattransfer surfaces to enable adequate temperature control. Agitation (orstirring) within the reactor can be accomplished with conventional andart-recognized agitators, static mixers, a circulation loop, etc. thatare fabricated from suitable corrosion resistant materials ofconstruction. Heat for the reaction can be applied internally orexternally to the reactor, or alternatively, by heating the chlorinatedalkane substrate.

The dehydrochlorination reaction is conducted in the liquid phase andunder substantially dry conditions, with some embodiments, because thepresence of water within the reactor (or reaction zone) can result ineither deactivation of the polyvalent antimony compound(s) and/or ferricchloride, with some embodiments. The presence of water in the reactor(or reaction zone) can cause the production of hydrochloric acid,because of the reaction of water with ferric chloride, polyvalentantimony chloride compounds, and/or the hydrogen chloride co-product,with some embodiments. Hydrochloric acid is an undesirable byproductthat can cause corrosion of vessels, piping, pumps and other equipmentthat would require the use of equipment made of more expensivehydrochloric acid resistant materials, with some embodiments.

With the dehydrochlorination reaction, the reactants (or reactioncomponents), such as, the chlorinated alkane substrate, polyvalentantimony compound(s), ferric chloride, optional solvent(s), etc.,charged to the reactor (or reaction zone) are substantially dry, such ascontaining less than 0.1 weight percent water, with some embodiments.The reactants and the reaction medium contain less than 1000 ppm ofwater, such as from 5 to 1000 ppm of water, with some furtherembodiments. The presence of water in the reactor before beginning theprocess (or water that enters the reactor subsequently due, for example,to process interruptions) can be expunged by purging the reactor with asubstantially dry or dried gas, such as dry nitrogen, hydrogen chlorideor chlorine, in accordance with some embodiments.

The reaction time for the dehydrochlorination reaction that is performedin accordance with the presently described process can vary, and candepend on various parameters, such as the temperature at which thereaction is performed, the amount and ratio of the polyvalent antimonychloride and ferric chloride used, the type of reaction vessel, and thedesired degree of conversion of the chlorinated alkane substrate, etc,with some embodiments. The dehydrochlorination reaction times can varyfrom 0.25 to 12 hours, or from 0.5 to 5 hours, when the reaction isperformed in a batch mode, with some embodiments.

The dehydrochlorination reaction can, with some embodiments, beperformed as a batch method, a continuous method, or a combinationthereof, such as a combination batch method(s) and continuous method(s).

When the dehydrochlorination reaction is performed in a continuous mode,the flow of reactants into the reactor, the reaction temperature, thereaction pressure, and the volumetric flow of effluents withdrawn fromthe reactor are chosen to also achieve the desired degree of conversionof the chlorinated alkane substrate to the corresponding alkene product,in accordance with some embodiments. When conducted in a continuousmode, the average residence time can vary from 0.25 to 12 hours, or from0.5 to 5 hours, with some embodiments. The average residence time isdefined as the reactor volume divided by the flow rate of chlorinatedalkane substrate in the dehydrochlorination reactor, in accordance withsome embodiments.

With both the batch and continuous modes, and in accordance with someembodiments, the dehydrochlorination reactor is associated withadditional process equipment, such as heating equipment (or means) toprovide heat to the reaction zone, such as by the heating of thechlorinated alkane substrate or by heating coils within the reactor,heat exchanger means to control the temperature of gases and effluentsremoved from the reactor (where required), gaseous effluent scrubbers,solid-liquid separators, and distillation columns to handle the hydrogenchloride co-product off-gas, the separation of the principal product(i.e., the alkene product) from any byproducts, and the separation ofthe catalyst(s) withdrawn along with liquid heavy byproducts.

With some embodiments of the dehydrochlorination reaction of the presentinvention, hydrogen chloride co-product effluent (usually as a gaseousstream) is removed, with some embodiments, from the reactor overhead andseparated, if necessary, from any uncondensed organic materials (such asalkene product and/or chlorinated alkane substrate) carried with it. Inaccordance with some further embodiments, the resultant recoveredhydrogen chloride is substantially anhydrous and can either: (a) befurther purified and used (or sold for use in other applications; or (b)dissolved in water and sold as hydrochloric acid; or (c) scrubbed withan alkali, such as sodium hydroxide, to neutralize the hydrogenchloride. The resultant alkali metal chloride salt, such as sodiumchloride, can, with some embodiments, be disposed of in anenvironmentally accepted manner or, in the case of sodium chloride, usedas feedstock to a chlorine-caustic electrolytic cell circuit.

In accordance with some embodiments of the dehydrochlorination reactionsof the present invention, a product stream effluent including crudealkene product (such as 1,1,2,3-tetrachloropropene) is, with someembodiments, removed from the reactor and optionally forwarded to adistillation zone containing one or more distillation columns (dependingon the composition of the product stream and the design of thedistillation column) after separating any solid catalyst component(s)(if necessary) carried with it. Byproducts from the distillation zoneare, with some embodiments, recycled to the process or disposed of in anenvironmentally accepted manner. In accordance with some embodiments,recovered polyvalent antimony compound(s), is optionally recycled backinto the process. Substantially pure alkene product (such as1,1,2,3-tetrachloropropene) is, with some embodiments obtained from thedistillation zone, with some embodiments. By “substantially pure alkeneproduct,” with some embodiments, means the collected or isolatedmaterial includes at least 90 percent by weight, or at least 95 percentby weight, or at least 99 percent by weight, or at least 99.5 percent byweight, or at least 99.9 percent by weight of alkene product, based ontotal weight of the collected (or isolated) material.

With some embodiments, the alkene product, of the various methods of thepresent invention, includes one or more polyvalent antimony compoundsand is a crude alkene product. The crude alkene product can, with someembodiments be used in further down-stream reactions, such as ahydrofluorination reaction, optionally after removal of iron chloride,such as ferric chloride, from the crude alkene product.

In accordance with some embodiments of the present invention, there isprovided a method of forming 1,1,2,3-tetrachloropropene by a processthat includes: in a first reaction, forming a crude product thatincludes 1,1,1,2,3-pentachloropropane and pentavalent antimonycompound(s); and in a second reaction, heating the crude product of thefirst reaction in the presence of ferric chloride, so as to form aproduct that includes 1,1,2,3-tetrachloropropene.

The method of forming 1,1,2,3-tetrachloropropene includes, with somefurther embodiments: (a) reacting, in a first reaction,1,1,1,3-tetrachloropropane with a source of chlorine in the presence ofa polyvalent antimony compound that includes a pentavalent antimonycompound, thereby forming a crude product that includes1,1,1,2,3-pentachloropropane and the pentavalent antimony compound; and(b) heating, in a second reaction, the crude product in the presence offerric chloride, thereby forming a product comprising1,1,2,3-tetrachloropropene.

The first reaction is, with some embodiments, conducted in accordancewith the chlorination reactions as described previously herein, whichinvolve reacting 1,1,1,3-tetrachloropropane with a source of chlorine inthe presence of a polyvalent antimony compound that includes apentavalent antimony compound, thereby forming a product that includes1,1,1,2,3-pentachloropropane. The second reaction is, with someembodiments, conducted in accordance with the dehydrochlorinationreactions as described previously herein, which involves heating achlorinated alkane substrate, such as 1,1,1,2,3-pentachloropropane, inthe presence of ferric chloride and a polyvalent antimony compound thatincludes a pentavalent antimony compound, thereby forming a product thatincludes the alkene product, such as 1,1,2,3-tetrachloropropene.

The source of chlorine is, with some embodiments, selected from chlorine(Cl₂) and/or sulfuryl chloride (SO₂Cl₂), as described previously herein.

The pentavalent antimony compound can, with some embodiments, includeone or more pentavalent antimony compounds represented by Formula (I) asdescribed previously herein. With some embodiments, the pentavalentantimony compound includes antimony pentachloride.

With some additional embodiments, the polyvalent antimony compound ofthe first reaction optionally further includes one or more trivalentantimony compounds. The trivalent antimony compounds can, with someembodiments, include one or more trivalent antimony compoundsrepresented by Formula (II) as described previously herein. With someembodiments, the trivalent antimony compound includes antimonytrichloride.

For purposes of non-limiting illustration, the method of preparing1,1,2,3-tetrachloropropene by a first reaction and a second reaction, inwhich the crude product of the first reaction is heated in the presenceof ferric chloride in the second reaction, in accordance with someembodiments of the present invention, is described with reference toFIG. 1. With reference to FIG. 1, there is depicted a process assembly 3that includes a chlorination reactor 11 and a dehydrochlorinationreactor 14. Through one or more conduits, such as conduit 17,1,1,1,3-tetrachloropropane, a source of chlorine, and a polyvalentantimony compound that includes a pentavalent antimony compound (and/ora precursor of the pentavalent antimony compound, as describedpreviously herein) are introduced into chlorination reactor 11. Thereaction components can be introduced into chlorination reactor 11together and/or at different times in any appropriate order.

Within chlorination reactor 11, the first reaction is conducted, inwhich 1,1,1,3-tetrachloropropane is reacted with a source of chlorine inthe presence of a polyvalent antimony compound that includes apentavalent antimony compound. The first reaction, within chlorinationreactor 11, results in the formation of a crude product that includes1,1,1,2,3-pentachloropropane, the pentavalent antimony compound, andoptionally one or more further polyvalent antimony compounds. Asdescribed previously herein, when a trivalent antimony compound ispresent in the first reaction, such as performed in reactor 11, at leasta portion of the trivalent antimony compound is converted into thecorresponding pentavalent antimony compound in the presence of thesource of chlorine.

The 1,1,1,3-tetrachloropropane, source of chlorine, and polyvalentantimony compound that includes a pentavalent antimony compound aremaintained within chlorination reactor 11, with some embodiments, atlevels (or amounts) in accordance with the description providedpreviously herein. With some embodiments, the chlorination reaction isconducted within chlorination reactor 11 with a mole ratio of chlorine(Cl₂) to 1,1,1,3-tetrachloropropane of from 0.2:1 to 1.5:1 or from 0.2:1to 1.1:1, and with a catalytic amount of polyvalent antimony compound.The polyvalent antimony compound can, with some embodiments, be presentwithin chlorination reactor 11 in a non-supported form (such as in aliquid form) and/or in a supported form (such as supported on a solidsupport), as described previously herein.

Chlorination reactor 11 can, with some embodiments, be equipped withagitation components (not shown), such as an impeller, for mixing thecontents of the chlorination reactor. Chlorination reactor 11 can, withsome further embodiments, be equipped with one or more internal and/orone or more external heat exchangers (not shown) for purposes ofcontrolling the temperature of the contents of the chlorination reactor.

The chlorination reaction is, with some embodiments, conducted withinchlorination reactor 11 in accordance with the description as providedpreviously herein. With some embodiments, the chlorination reaction isconducted within chlorination reactor 11 at a temperature of at least40° C., such as from 40° C. to 200° C., and a pressure of at least 1psia, such as from 1 psia to 500 psia.

The first reaction conducted within chlorination reactor 11, with someembodiments, results in the formation of a crude product that includes1,1,1,2,3-pentachloropropane and hydrogen chloride (HCl). With someembodiments, the hydrogen chloride is produced in a gaseous form, and isremoved from chlorination reactor 11 through one or more appropriateconduits, such as conduit 20. The hydrogen chloride can, with someembodiments, be forwarded through conduit 20 for disposal and/or to oneor more treatment apparatuses, such as a one or more scrubbers (notshown), as described previously herein, or further purified and used (orsold for use) in other applications.

The crude product formed within chlorination reactor 11, includes withsome embodiments, 1,1,1,2,3-pentachloropropane, one or more pentavalentantimony compounds, such as antimony pentachloride, optionally one ormore trivalent antimony compounds, such as antimony trichloride, and1,1,1,3-tetrachloropropane. With some embodiments, the1,1,1,3-tetrachloropropane is present in the crude product of the firstreaction in an amount of less than 1 percent by weight, based on thetotal weight of the crude product.

The crude product formed within chlorination reactor 11, which includes1,1,1,2,3-pentachloropropane and one or more pentavalent antimonycompounds is forwarded through one or more appropriate conduits, such asconduit 23, to dehydrochlorination reactor 14. Withindehydrochlorination reactor 14 the second reaction is performed byheating the crude product (from the first reaction) in the presence offerric chloride, so as to form a product that includes1,1,2,3-tetrachloropropene.

Dehydrochlorination reactor 14 can, with some embodiments, be equippedwith agitation components (not shown), such as an impeller, for mixingthe contents of the dehydrochlorination reactor. Dehydrochlorinationreactor 14 can, with some further embodiments, be equipped with one ormore internal heat exchangers and/or one or more external heatexchangers (not shown) for purposes of controlling the temperature ofthe contents of the dehydrochlorination reactor.

The second reaction, which is performed in dehydrochlorination reactor14, is conducted, with some embodiments, in accordance with thedescription as provided previously herein with regard to the method offorming an alkene product, such as 1,1,2,3-tetrachloropropene from1,1,1,2,3-pentachloropropane. In accordance with some embodiments, thesecond reaction is performed in dehydrochlorination reactor 14 at atemperature of at least 50° C., such as from 50° C. to 200° C., and apressure of at least 0.6 psia, such as from 0.6 psia to 215 psia. Withsome further embodiments, the second reaction is conducted in thedehydrochlorination reactor 14 with a mole ratio of ferric chloride topolyvalent antimony compound of from 1000:1 to 1:1000.

Ferric chloride can, with some embodiments, be periodically orcontinuously introduced into dehydrochlorination reactor 14 through oneor more appropriate conduits, such as conduit 26.

The second reaction conducted within dehydrochlorination reactor 14,which some embodiments, results in the co-production of hydrogenchloride (HCl). The hydrogen chloride, with some embodiments, is formedas gaseous hydrogen chloride, which is removed from chlorination reactor14 by one or more appropriate conduits, such as conduit 29. The hydrogenchloride can, with some embodiments, be forwarded through conduit 29 fordisposal and/or to one or more treatment apparatuses, such as a one ormore scrubbers (not shown), as described previously herein, or furtherpurified and used (or sold for use) in other applications.

The product formed from the second reaction that is conducted withindehydrochlorination reactor 14, and which includes1,1,2,3-tetrachloropropene can, with some embodiments, be removed fromdehydrochlorination reactor 14, such as through conduit 32, andforwarded to storage and/or additional processing steps, such aspurification and/or isolation processing steps.

The product formed from the second reaction, includes, with someembodiments, 1,1,2,3-tetrachloropropene, antimony pentachloride, andantimony trichloride, and the method further includes, distilling theproduct, thereby forming: (i) a tops product including1,1,2,3-tetrachloropropene; and (ii) a bottoms product including1,1,1,2,3-pentachloropropane, antimony pentachloride, antimonytrichloride. If present in the product of the second reaction and thebottoms product (of distillation), the antimony pentachloride is, withsome embodiments, present in an amount of less than 100 ppm, by weight.With some embodiments, a further distillation apparatus, such as a flashdistillation apparatus, is used to remove ferric chloride prior to thedistillation of the product of the second reaction, as described infurther detail herein.

With some embodiments, at least a portion of the bottoms product (whichincludes 1,1,1,2,3-pentachloropropane and antimony trichloride) isintroduced into the first reaction.

With further reference to FIG. 1, a product of the second reaction,which is performed within dehydrochlorination reactor 14, which includes1,1,2,3-tetrachloropropene, antimony pentachloride, and antimonytrichloride is forwarded through conduit 32 to a first distillationcolumn 35 where it is subjected to distillation. Distilling of suchproduct within first distillation column 35 results in the formation of:(i) a tops product that includes 1,1,2,3-tetrachloropropene, which isremoved from first distillation column 35 through a conduit 38; and (ii)a bottoms product that includes 1,1,1,2,3-pentachloropropane, optionallyantimony pentachloride, and antimony trichloride, which is removed fromfirst distillation column 35 through a conduit 41. The tops product thatincludes 1,1,2,3-tetrachloropropene can be forwarded through conduit 38to a storage tank (not shown) and/or to further processing steps, suchas further purification and/or isolation steps.

With some embodiments, a further distillation apparatus (not shown),such as a flash distillation apparatus, is included in-line with conduit32 between dehydrochlorination reactor 14 and distillation column 35 forpurposes of removing ferric chloride, so as to prevent the introductionof ferric chloride into distillation column 35.

With some embodiments, at least a portion of the bottoms product thatincludes 1,1,1,2,3-pentachloropropane, antimony pentachloride, andantimony trichloride that is removed from first distillation column 35through conduit 41 is forwarded through conduit 44 and introduced intothe first reaction, which is conducted in chlorination reactor 11. Whilenot intending to be bound by any theory, it is believed that at least aportion of the antimony trichloride within the bottoms product that isintroduced into the first reaction in chlorination reactor 11 isconverted to antimony pentachloride in the presence of the source ofchlorine that is present within chlorination reactor 11.

In accordance with some embodiments of the present invention, the secondreaction is conducted at a temperature and a pressure whereby at least aportion of the product is converted to a vaporous product that includesvaporous 1,1,2,3-tetrachloropropene. The method of the present inventionthen further includes: (i) removing vaporous product that includesvaporous 1,1,2,3-tetrachloropropene from the second reaction; and (ii)condensing the vaporous product removed from the second reaction intoliquid product that includes liquid 1,1,2,3-tetrachloropropene. Theformation of the vaporous product, and removal and condensation thereofis with some embodiments referred to as a reactive distillation process,which with some further embodiments is conducted continuously.

For purposes of non-limiting illustration of embodiments of the presentinvention, in which the second reaction is conducted so as to form avaporous product, which is removed and condensed, further reference toFIG. 1 is made. The second reaction, which is conducted withindehydrochlorination reactor 14, is conducted at a temperature and apressure whereby at least a portion of the product is converted to avaporous product that includes 1,1,2,3-tetrachloropropene. Thetemperature and pressure can, with some embodiments, be selected fromthose temperatures, pressures and ranges as discussed previously herein.With some embodiments, the second reaction is conducted at a temperatureof from 50° C. to 200° C., and a pressure of from 0.6 psia to 215 psia.

The vaporous product, which includes 1,1,2,3-tetrachloropropene, isremoved from the second reaction and the dehydrochlorination reactor 14through one or more appropriate conduits, such as conduit 29. With someembodiments, when vaporous product is removed through conduit 29,product of the second reaction is not removed through conduit 32. Withsome further embodiments, when vaporous product is removed throughconduit 29, some product of the second reaction is also removed throughconduit 32. With some embodiments of the present invention, reactor 14is periodically purged to remove spent materials therefrom, such as, butnot limited to, spent iron compounds, through one or more conduits (notshown).

The vaporous product, which includes 1,1,2,3-tetrachloropropene, isforwarded through conduit 29 and into condenser 47. Within condenser 47the vaporous product is condensed into liquid product that includesliquid 1,1,2,3-tetrachloropropene. The condensed liquid product thatincludes liquid 1,1,2,3-tetrachloropropene is removed from condenser 47through one or more appropriate conduits, such as through conduit 50.The condensed liquid product can, with some embodiments, be forwardedthrough conduit 50 to a storage tank (not shown), and/or to furtherprocessing steps, such as isolation and/or purification steps. With someembodiments, the condensed liquid product is removed from condenser 47and forwarded through conduit 50 to first distillation column 35, inwhich the condensed liquid product is distilled so as to form a topsproduct that includes 1,1,2,3-tetrachloropropene, which is removed fromfirst distillation column 35 and forwarded through conduit 38, and abottoms product that includes other materials, which is removed fromfirst distillation column 35 and forwarded through conduit 41.

As discussed previously herein, the second reaction conducted withindehydrochlorination reactor 14, which some embodiments, results in theco-production of gaseous hydrogen chloride (HCl). The gaseous hydrogenchloride is, with some embodiments, removed from dehydrochlorinationreactor 14 and forwarded through conduit 29 and into condenser 47.Condenser 47 is, with some embodiments, operated under conditions suchthat the gaseous hydrogen chloride, introduced therein through conduit29, does not condense. Gaseous hydrogen chloride thus, with someembodiments, passes through condenser 47 and is removed therefromthrough conduit 30.

With some embodiments, the vaporous product of the second reactionformed within dehydrochlorination reactor 14 includes, vaporous1,1,2,3-tetrachloropropene, vaporous 1,1,1,2,3-pentachloropropane,vaporous antimony pentachloride, and vaporous antimony trichloride. Thismulticomponent vaporous product is, with some embodiments, removed fromthe second reaction and dehydrochlorination reactor 14 through conduit29 and forwarded through conduit 29 into condenser 47. Within condenser47, the multicomponent vaporous product is condensed into amulticomponent liquid product that includes liquid1,1,2,3-tetrachloropropene, liquid 1,1,1,2,3-pentachloropropane, liquidantimony pentachloride, and liquid antimony trichloride. The condensedmulticomponent liquid product, with some embodiments, is removed fromcondenser 47 and forwarded through conduit 50 to a storage tank (notshown) and/or to further processing steps, such as isolation and/orpurification steps.

With some embodiment, the condensed multicomponent liquid product, isremoved from condenser 47 and forwarded through conduit 50 to firstdistillation column 35. Within first distillation column 35, thecondensed multicomponent liquid product is distilled so as to form: (i)a tops product that includes 1,1,2,3-tetrachloropropene; and (ii) abottom product that includes 1,1,1,2,3-pentachloropropane, antimonytrichloride, and antimony pentachloride. The tops product that includes1,1,2,3-tetrachloropropene is removed from first distillation column 35and forwarded through conduit 38 to a storage tank (not shown) and/or tofurther processing steps, as described previously herein. The bottomsproduct is removed from first distillation column 35 and forwardedthrough conduit 41 to a storage tank (not shown) and/or to furtherprocessing steps, as described previously herein. With some embodiments,at least a portion of the bottoms product removed from firstdistillation column 35 through conduit 41 is forwarded through conduit44 to chlorination reactor 11 where it is introduced into the firstreaction, as described previously herein.

The tops product that includes 1,1,2,3-tetrachloropropene, which isremoved from first distillation column 35 through conduit 38 is, withsome embodiments, forwarded through conduit 38 to a second distillationcolumn 53. The tops product removed from first distillation column 35,with some embodiments, includes 1,1,2,3-tetrachloropropene and one ormore materials having a boiling point lower than that of1,1,2,3-tetrachloropropene, which are referred to as lights. With someembodiments, the lights include 1,1,3,3-tetrachloropropene,1,1,3-trichloropropene, and/or 1,1,1,3-tetrachloropropane. Distillationof the tops product within second distillation column 53 results in theformation of: (i) a second tops product, which includes the lights and(ii) a second bottoms product, which includes purified1,1,2,3-tetrachloropropene, which is removed from second distillationcolumn 53 and forwarded through conduit 59. The second tops product,which contains the lights, is, with some embodiments, forwarded throughconduit 56 to a storage tank (not shown) and/or to further processingand/or disposal. The second bottoms product which includes purified1,1,2,3-tetrachloropropene, is, with some embodiments, forwarded throughconduit 59 to a storage tank (not shown) and/or further processingsteps.

The method of the present invention, which involves preparing1,1,2,3-tetrachloropropene by a first reaction and a second reaction, inwhich the crude product of the first reaction is heated in the presenceof ferric chloride in the second reaction, is, with some embodiments,conducted as a batch method and/or a continuous method.

The method of the present invention, which involves preparing1,1,2,3-tetrachloropropene by a first reaction and a second reaction, inwhich the crude product of the first reaction is heated in the presenceof ferric chloride in the second reaction, includes, with someembodiments, forming 1,1,1,3-tetrachloropropane (which is used in thefirst reaction) by reacting carbon tetrachloride with ethylene in thepresence of an iron chloride, iron metal, and a trialkylphosphate, inaccordance with the description provided previously herein.

In accordance with some embodiments of the present invention,1,1,2,3-tetrachloropropene is prepared by a process that includes:forming, in a first reaction, a crude product that includes1,1,1,2,3-pentachloropropane; distilling the crude product to form abottoms product that includes 1,1,1,2,3-pentachloropropane and antimonytrichloride; introducing a source of chlorine into the bottoms product,so as to convert at least a portion of the antimony trichloride toantimony pentachloride, and thereby forming a modified bottoms product;and heating, in a second reaction, the modified bottoms product in thepresence of ferric chloride, so as to form a product that includes1,1,2,3-tetrachloropropene.

The method of forming 1,1,2,3-tetrachloropropene includes, with somefurther embodiments: (a) reacting, in a first reaction,1,1,1,3-tetrachloropropane with a source of chlorine in the presence ofa pentavalent antimony compound that includes antimony pentachloride,thereby forming a crude product that includes1,1,1,2,3-pentachloropropane, 1,1,1,3-tetrachloropropane, antimonypentachloride, and antimony trichloride; (b) distilling the crudeproduct thereby forming, (i) a tops product that includes1,1,1,3-tetrachloropropane and antimony pentachloride, and (ii) abottoms product that includes 1,1,1,2,3-pentachloropropane and antimonytrichloride; (c) introducing a source of chlorine into the bottomsproduct, thereby converting at least a portion of the antimonytrichloride to antimony pentachloride, thereby forming a modifiedbottoms product; and (d) heating, in a second reaction, the modifiedbottoms product in the presence of ferric chloride, thereby forming aproduct that includes 1,1,2,3-tetrachloropropene.

The first reaction is, with some embodiments, conducted in accordancewith the chlorination reactions as described previously herein, whichinvolve reacting 1,1,1,3-tetrachloropropane with a source of chlorine inthe presence of a polyvalent antimony compound that includes apentavalent antimony compound, such as antimony pentachloride, therebyforming a product that includes 1,1,1,2,3-pentachloropropane. The secondreaction is, with some embodiments, conducted in accordance with thedehydrochlorination reactions as described previously herein, whichinvolves heating a chlorinated alkane substrate, such as1,1,1,2,3-pentachloropropane, in the presence of ferric chloride and apolyvalent antimony compound that includes a pentavalent antimonycompound, such as antimony pentachloride, thereby forming a product thatincludes the alkene product, such as 1,1,2,3-tetrachloropropene.

The source of chlorine is, with some embodiments, selected from chlorine(Cl₂) and/or sulfuryl chloride (SO₂Cl₂), as described previously herein.

The pentavalent antimony compound can, with some embodiments, furtherinclude one or more pentavalent antimony compounds represented byFormula (I) as described previously herein.

With some additional embodiments, the first reaction optionally furtherincludes one or more trivalent antimony compounds. The trivalentantimony compounds can, with some embodiments, include one or moretrivalent antimony compounds represented by Formula (II) as describedpreviously herein. With some embodiments, the trivalent antimonycompound includes antimony trichloride.

For purposes of non-limiting illustration, the method of preparing1,1,2,3-tetrachloropropene by a first reaction and a second reaction, inwhich a modified bottoms product, obtained by distillation of the crudeproduct of the first reaction, is heated in the presence of ferricchloride in the second reaction, in accordance with some embodiments ofthe present invention, is described with reference to FIG. 2. Withreference to FIG. 2, there is depicted a process assembly 5 thatincludes a chlorination reactor 11 and a dehydrochlorination reactor 14.Through one or more conduits, such as conduit 17,1,1,1,3-tetrachloropropane, a source of chlorine, and a pentavalentantimony compound that includes antimony pentachloride (and/or aprecursor of antimony pentachloride, as described previously herein) areintroduced into chlorination reactor 11. The reaction components can beintroduced into chlorination reactor 11 together and/or at differenttimes in any appropriate order.

Within chlorination reactor 11, the first reaction is conducted, inwhich 1,1,1,3-tetrachloropropane is reacted with a source of chlorine inthe presence of a pentavalent antimony compound that includes antimonypentachloride. The first reaction, within chlorination reactor 11results in the formation of a crude product that includes1,1,1,2,3-pentachloropropane, 1,1,1,3-tetrachloropropane, antimonypentachloride, and antimony trichloride.

The 1,1,1,3-tetrachloropropane, source of chlorine, and pentavalentantimony compound that includes antimony pentachloride are maintainedwithin chlorination reactor 11, with some embodiments, at levels (oramounts) in accordance with the description provided previously herein.With some embodiments, the first reaction (or chlorination reaction) isconducted within chlorination reactor 11 with a mole ratio of chlorine(Cl₂) to 1,1,1,3-tetrachloropropane of from 0.2:1 to 1.5:1 or from 0.2:1to 1.1:1, and with a catalytic amount of pentavalent antimonycompound(s).

Chlorination reactor 11 can, with some embodiments, be equipped withagitation components (not shown), such as an impeller, for mixing thecontents of the chlorination reactor. Chlorination reactor 11 can, withsome further embodiments, be equipped with one or more internal and/orone or more external heat exchangers (not shown) for purposes ofcontrolling the temperature of the contents of the chlorination reactor.

The first (or chlorination) reaction is, with some embodiments,conducted within chlorination reactor 11 in accordance with thedescription as provided previously herein. With some embodiments, thefirst (or chlorination) reaction is conducted within chlorinationreactor 11 at a temperature of at least 40° C., such as from 40° C. to200° C., and a pressure of at least 1 psia, such as from 1 psia to 500psia.

The first reaction conducted within chlorination reactor 11, with someembodiments, results in the formation of the crude product and hydrogenchloride (HCl). With some embodiments, the hydrogen chloride is producedin a gaseous form, and is removed from chlorination reactor 11 throughone or more appropriate conduits, such as conduit 20. The hydrogenchloride can, with some embodiments, be forwarded through conduit 20 fordisposal and/or to one or more treatment apparatuses, such as a one ormore scrubbers (not shown), as described previously herein, or furtherpurified and used (or sold for use) in other applications.

The crude product formed within chlorination reactor 11, which includes1,1,1,2,3-pentachloropropane, 1,1,1,3-tetrachloropropane, antimonypentachloride, and antimony trichloride, is forwarded through one ormore appropriate conduits, such as conduit 23, to a first distillationcolumn 62. Within first distillation column 62, the crude product of thefirst reaction is distilled so as to form; (i) a tops product thatincludes 1,1,1,3-tetrachloropropane and antimony pentachloride; and (ii)a bottoms product that includes 1,1,1,2,3-pentachloropropane andantimony trichloride.

The tops product, with some embodiments, is removed from firstdistillation column 62 and forwarded through conduit 65 to a storagetank (not shown) and/or one or more additional processing steps, such asisolation and/or purification steps. With some embodiments, at least aportion of the tops product, which includes 1,1,1,3-tetrachloropropaneand antimony pentachloride, is introduced into the first reaction. Withreference to FIG. 2, at least a portion of the tops product removed fromfirst distillation column 62 through conduit 65 is forwarded throughconduit 68 and introduced into the first reaction in chlorinationreactor 11.

With further reference to FIG. 2, the bottoms product is removed fromfirst distillation column 62 and forwarded through conduit 71. A sourceof chlorine is introduced into the bottoms product, with someembodiments, through a conduit 74 that intersects with conduit 71.Introduction of the source of chlorine into the bottoms product as itpasses through conduit 71 results in conversion of at least a portion ofthe antimony trichloride to antimony pentachloride, thereby forming amodified bottoms product. The modified bottoms product includes, withsome embodiments, 1,1,1,2,3-pentachloropropane, antimony pentachloride,and optionally antimony trichloride.

With some embodiments, the modified bottoms product is substantiallyfree of the source of chlorine that was introduced into the bottomsproduct. Minimizing or eliminating the amount of source chlorine in themodified bottoms product is desirable, with some embodiments, because itcan interfere with the formation of the desired1,1,2,3-tetrachloropropene product. With some embodiments, the modifiedbottoms product includes less than 1000 ppm of the source of chlorinethat was introduced into the bottoms product.

The modified bottoms product is further forwarded through conduit 71,past the intersection point with conduit 74, and introduced intodehydrochlorination reactor 14, where the second reaction is conducted.

The second reaction is, with some embodiments, conducted withindehydrochlorination reactor 14 of FIG. 2 in accordance with thedescription provided previously herein with regard to FIG. 1. Withindehydrochlorination reactor 14 the second reaction is performed byheating the modified bottoms product (obtained from distillation of thecrude product of the first reaction) in the presence of ferric chloride,so as to form a product that includes 1,1,2,3-tetrachloropropene.

Dehydrochlorination reactor 14 of FIG. 2 can, with some embodiments, beequipped with agitation components (not shown), such as an impeller, formixing the contents of the dehydrochlorination reactor.Dehydrochlorination reactor 14 can, with some further embodiments, beequipped with one or more internal and/or one or more external heatexchangers (not shown) for purposes of controlling the temperature ofthe contents of the dehydrochlorination reactor.

The second reaction, which is performed in dehydrochlorination reactor14, is conducted, with some embodiments, in accordance with thedescription as provided previously herein with regard to the method offorming an alkene product, such as 1,1,2,3-tetrachloropropene from1,1,1,2,3-pentachloropropane. In accordance with some embodiments, thesecond reaction is performed in dehydrochlorination reactor 14 of FIG. 2at a temperature of at least 50° C., such as from 50° C. to 200° C., anda pressure of at least 0.6 psia, such as from 0.6 psia to 215 psia. Withsome further embodiments, the second reaction is conducted in thedehydrochlorination reactor 14 of FIG. 2 with a mole ratio of ferricchloride to polyvalent antimony compound of from 1000:1 to 1:1000.

Ferric chloride is, with some embodiments, periodically or continuouslyintroduced into dehydrochlorination reactor 14 through one or moreappropriate conduits, such as conduit 26.

The second reaction conducted within dehydrochlorination reactor 14,with some embodiments, results in the co-production of hydrogen chloride(HCl). The hydrogen chloride, with some embodiments, is formed asgaseous hydrogen chloride, which is removed from chlorination reactor 14by one or more appropriate conduits, such as conduit 29. The hydrogenchloride can, with some embodiments, be forwarded through conduit 29 fordisposal and/or to one or more treatment apparatuses, such as a one ormore scrubbers (not shown), as described previously herein, or furtherpurified and used (or sold for use) in other applications.

The product formed from the second reaction that is conducted withindehydrochlorination reactor 14, and which includes1,1,2,3-tetrachloropropene can, with some embodiments, be removed fromdehydrochlorination reactor 14, such as through conduit 32, andforwarded to storage and/or additional processing steps, such aspurification and/or isolation processing steps.

The product formed from the second reaction, includes, with someembodiments, 1,1,2,3-tetrachloropropene, antimony pentachloride, andantimony trichloride, and the method further includes, distilling theproduct, thereby forming: (i) a second tops product including1,1,2,3-tetrachloropropene; and (ii) a second bottoms product including1,1,1,2,3-pentachloropropane and antimony trichloride. The secondbottoms product can, with some embodiments, include antimonypentachloride, which if present, is typically present in an amount ofless than 100 ppm by weight. With some embodiments, a furtherdistillation apparatus, such as a flash distillation apparatus, is usedto remove ferric chloride prior to the distillation of the product ofthe second reaction, as described in further detail herein.

With some embodiments, at least a portion of the second bottoms product(which includes 1,1,1,2,3-pentachloropropane and antimony trichloride)is introduced into the first reaction.

With further reference to FIG. 2, a product of the second reaction,which is performed within dehydrochlorination reactor 14, which includes1,1,2,3-tetrachloropropene, antimony pentachloride, and antimonytrichloride is forwarded through conduit 32 to a second distillationcolumn 35′ where it is subjected to distillation. Distilling of suchproduct within second distillation column 35′ results in the formationof: (i) a second tops product that includes 1,1,2,3-tetrachloropropene,which is removed from second distillation column 35′ through a conduit38′; and (ii) a second bottoms product that includes1,1,1,2,3-pentachloropropane and antimony trichloride, which is removedfrom second distillation column 35′ through a conduit 41′. The secondtops product that includes 1,1,2,3-tetrachloropropene can be forwardedthrough conduit 38′ to a storage tank (not shown) and/or to furtherprocessing steps, such as further purification and/or isolation steps.

With some embodiments, a further distillation apparatus (not shown),such as a flash distillation apparatus, is included in-line with conduit32 between dehydrochlorination reactor 14 and second distillation column35′ for purposes of removing ferric chloride, so as to prevent theintroduction of ferric chloride into second distillation column 35′.

With some embodiments, at least a portion of the second bottoms productthat includes 1,1,1,2,3-pentachloropropane and antimony trichloride thatis removed from second distillation column 35′ through conduit 41′ isforwarded through conduit 44′ and introduced into the first reaction,which is conducted in chlorination reactor 11. While not intending to bebound by any theory, it is believed that at least a portion of theantimony trichloride within the second bottoms product that isintroduced into the first reaction in chlorination reactor 11 isconverted to antimony pentachloride in the presence of the source ofchlorine that is present within chlorination reactor 11.

In accordance with some embodiments of the present invention, the secondreaction is conducted at a temperature and a pressure whereby at least aportion of the product is converted to a vaporous product that includesvaporous 1,1,2,3-tetrachloropropene. The method then further includes:(i) removing vaporous product that includes vaporous1,1,2,3-tetrachloropropene from the second reaction; and (ii) condensingthe vaporous product removed from the second reaction into liquidproduct that includes liquid 1,1,2,3-tetrachloropropene. The formationof the vaporous product, and removal and condensation thereof is withsome embodiments referred to as a reactive distillation process, whichwith some further embodiments is conducted continuously.

For purposes of non-limiting illustration of embodiments of the presentinvention, in which the second reaction is conducted so as to form avaporous product, which is removed and condensed, further reference toFIG. 2 is made. The second reaction, which is conducted withindehydrochlorination reactor 14, is conducted at a temperature and apressure whereby at least a portion of the product is converted to avaporous product that includes 1,1,2,3-tetrachloropropene. Thetemperature and pressure can, with some embodiments, be selected fromthose temperatures, pressures and ranges as discussed previously herein.With some embodiments, the second reaction is conducted at a temperatureof from 50° C. to 200° C., and a pressure of from 0.6 psia to 215 psia.

With reference to FIG. 2, the vaporous product, which includes1,1,2,3-tetrachloropropene, is removed from the second reaction and thedehydrochlorination reactor 14 through one or more appropriate conduits,such as conduit 29. With some embodiments, when vaporous product isremoved through conduit 29, the product of the second reaction is notremoved through conduit 32. With some further embodiments, when vaporousproduct is removed through conduit 29, some of the product of the secondreaction is also removed through conduit 32. With some embodiments ofthe present invention, dehydrochlorination reactor 14 is periodicallypurged to remove spent materials therefrom, such as, but not limited to,spent iron compounds, through one or more conduits (not shown).

With further reference to FIG. 2, the vaporous product, which includes1,1,2,3-tetrachloropropene, is forwarded through conduit 29 and intocondenser 47. Within condenser 47 the vaporous product is condensed intoliquid product that includes liquid 1,1,2,3-tetrachloropropene. Thecondensed liquid product that includes liquid 1,1,2,3-tetrachloropropeneis removed from condenser 47 through one or more appropriate conduits,such as through conduit 50. The condensed liquid product can, with someembodiments, be forwarded through conduit 50 to a storage tank (notshown), and/or to further processing steps, such as isolation and/orpurification steps. With some embodiments, the condensed liquid productis removed from condenser 47 and forwarded through conduit 50 to seconddistillation column 35′, in which the condensed liquid product isdistilled so as to form a second tops product that includes1,1,2,3-tetrachloropropene, which is removed from second distillationcolumn 35′ and forwarded through conduit 38′, and a second bottomsproduct that includes other materials, which is removed from seconddistillation column 35′ and forwarded through conduit 41′.

As discussed previously herein and with further reference to FIG. 2, thesecond reaction as conducted within dehydrochlorination reactor 14, withsome embodiments, results in the co-production of gaseous hydrogenchloride (HCl). The gaseous hydrogen chloride is, with some embodiments,removed from dehydrochlorination reactor 14 and forwarded throughconduit 29 and into condenser 47. Condenser 47 is, with someembodiments, operated under conditions such that the gaseous hydrogenchloride, introduced therein through conduit 29, does not condense.Gaseous hydrogen chloride thus, with some embodiments, passes throughcondenser 47 and is removed therefrom through conduit 30.

With some embodiments and with further reference to FIG. 2, the vaporousproduct of the second reaction formed within dehydrochlorination reactor14 includes, vaporous 1,1,2,3-tetrachloropropene, vaporous1,1,1,2,3-pentachloropropane, vaporous antimony pentachloride, andvaporous antimony trichloride. This multicomponent vaporous product is,with some embodiments, removed from the second reaction anddehydrochlorination reactor 14 through conduit 29 and forwarded throughconduit 29 into condenser 47. Within condenser 47, the multicomponentvaporous product is condensed into a multicomponent liquid product thatincludes liquid 1,1,2,3-tetrachloropropene, liquid1,1,1,2,3-pentachloropropane, liquid antimony pentachloride, and liquidantimony trichloride. The condensed multicomponent liquid product, withsome embodiments, is removed from condenser 47 and forwarded throughconduit 50 to a storage tank (not shown) and/or to further processingsteps, such as isolation and/or purification steps.

With some embodiments and with further reference to FIG. 2, thecondensed multicomponent liquid product, is removed from condenser 47and forwarded through conduit 50 to second distillation column 35′.Within second distillation column 35′, the condensed multicomponentliquid product is distilled so as to form: (i) a second tops productthat includes 1,1,2,3-tetrachloropropene; and (ii) a second bottomsproduct that includes 1,1,1,2,3-pentachloropropane, antimonytrichloride, and antimony pentachloride. The second tops product thatincludes 1,1,2,3-tetrachloropropene is removed from second distillationcolumn 35′ and forwarded through conduit 38′ to a storage tank (notshown) and/or to further processing steps, as described previouslyherein. The second bottoms product is removed from second distillationcolumn 35′ and forwarded through conduit 41′ to a storage tank (notshown) and/or to further processing steps, as described previouslyherein. With some embodiments, at least a portion of the second bottomsproduct removed from second distillation column 35′ through conduit 41′is forwarded through conduit 44′ to chlorination reactor 11 where it isintroduced into the first reaction, as described previously herein.

With further reference to FIG. 2, the second tops product that includes1,1,2,3-tetrachloropropene, which is removed from second distillationcolumn 35′ through conduit 38′ is, with some embodiments, forwardedthrough conduit 38′ to a third distillation column 77. The second topsproduct removed from second distillation column 35′, with someembodiments, includes 1,1,2,3-tetrachloropropene and one or morematerials having a boiling point lower than that of1,1,2,3-tetrachloropropene, which are referred to as lights. With someembodiments, the lights include 1,1,3,3-tetrachloropropene,1,1,3-trichloropropene, and/or 1,1,1,3-tetrachloropropane. Distillationof the second tops product within third distillation column 77 resultsin the formation of: (i) a third tops product, which includes the lightsand (ii) a third bottoms product, which includes purified1,1,2,3-tetrachloropropene, which is removed from third distillationcolumn 77 and forwarded through conduit 83. The third tops product,which contains the lights, is, with some embodiments, forwarded throughconduit 80 to a storage tank (not shown) and/or to further processingand/or disposal. The third bottoms product which includes purified1,1,2,3-tetrachloropropene, is, with some embodiments, forwarded throughconduit 83 to a storage tank (not shown) and/or further processingsteps.

The method of preparing 1,1,2,3-tetrachloropropene by a first reactionand a second reaction, in which a modified bottoms product, obtained bydistillation of the crude product of the first reaction, is heated inthe presence of ferric chloride in the second reaction, in accordancewith some embodiments of the present invention, is conducted as acontinuous method and/or a batch method.

The method of the present invention, which involves preparing1,1,2,3-tetrachloropropene by a first reaction and a second reaction, inwhich a modified bottoms product, obtained by distillation of the crudeproduct of the first reaction, is heated in the presence of ferricchloride in the second reaction, in accordance with some embodiments ofthe present invention, includes with some embodiments, forming1,1,1,3-tetrachloropropane (which is used in the first reaction) byreacting carbon tetrachloride with ethylene in the presence of an ironchloride, iron metal, and a trialkylphosphate, in accordance with thedescription provided previously herein.

In some embodiments, there is provided a method of forming an alkeneproduct comprising, heating a chlorinated alkane substrate in thepresence of at least one polyvalent antimony compound comprising atleast one pentavalent antimony compound, thereby forming a productcomprising said alkene product, wherein said alkene product optionallyhas at least one chlorine group covalently bonded thereto, and saidchlorinated alkane substrate and said alkene product each have a carbonbackbone structure that is in each case the same. Suitable alkeneproducts, chlorinated alkane substrates, polyvalent antimony compoundsand other optional components are discussed in detail above. Suitableamounts of the components and other optional components are discussed indetail above. Suitable processing conditions are discussed in detailabove.

In some embodiments, the heating of the chlorinated alkane substrate inthe presence of the at least one polyvalent antimony compound issubstantially free of iron chloride, iron metal, and/ortrialkylphosphate. In some embodiments, the heating of the chlorinatedalkane substrate in the presence of the at least one polyvalent antimonycompound is conducted in the presence of less than about 5 weightpercent of iron chloride, iron metal, and/or trialkylphosphate, on abasis of weight of chlorinated alkane substrate. In some embodiments,the heating of the chlorinated alkane substrate in the presence of theat least one polyvalent antimony compound is conducted in the presenceof less than about 1 weight percent of iron chloride, iron metal, and/ortrialkylphosphate, on a basis of weight of chlorinated alkane substrate.In some embodiments, the heating of the chlorinated alkane substrate inthe presence of the at least one polyvalent antimony compound isconducted in the presence of less than about 0.1 weight percent of ironchloride, iron metal, and/or trialkylphosphate, on a basis of weight ofchlorinated alkane substrate.

In some embodiments, the heating of the chlorinated alkane substrate inthe presence of the at least one polyvalent antimony compound comprisinga pentavalent antimony compound to thereby form a product comprisingsaid alkene product is conducted in the absence of iron chloride, ironmetal, and/or trialkylphosphate. In some embodiments, the heating of thechlorinated alkane substrate is conducted in the presence of the atleast one polyvalent antimony compound as the sole catalyst present inthe reaction. Such iron chlorides, iron metals, and/ortrialkylphosphates are discussed in detail above. In some embodiments,the iron chloride comprises ferric chloride and/or ferrous chloride.

In some embodiments, the pentavalent antimony compound comprises one ormore pentavalent antimony compounds represented by the following Formula(I),Sb(R¹)_(a)(Cl)_(b)  (I)wherein the sum of a and b is 5, provided that b is at least 2, andR¹ independently for each a is selected from the group consisting oflinear, branched, or cyclic alkyl, and aryl. In some embodiments, thepentavalent antimony compound comprises antimony pentachloride

In some embodiments, the heating of 1,1,1,3,3-pentachloropropane iscarried out in the presence of at least one polyvalent antimony compoundcomprising at least one pentavalent antimony compound and1,1,1,2,3-pentachloropropane.

In some embodiments, there is provided a method of preparing1,1,1,2,3-pentachloropropane comprising, reacting1,1,1,3-tetrachloropropane with a source of chlorine in the presence ofa polyvalent antimony compound comprising a pentavalent antimonycompound and substantially free of iron chloride, iron metal, and/ortrialkylphosphate, thereby forming a product comprising1,1,1,2,3-pentachloropropane.

In some embodiments, there is provided a method of forming1,1,3,3-tetrachloropropene comprising heating1,1,1,3,3-pentachloropropane in the presence of at least one polyvalentantimony compound comprising at least one pentavalent antimony compound,thereby forming 1,1,3,3-tetrachloropropene. Suitable polyvalent antimonycompounds and other optional components are discussed in detail above.Suitable amounts of the components and other optional components arediscussed in detail above. Suitable processing conditions are discussedin detail above.

In some embodiments, the heating of the 1,1,1,3,3-pentachloropropane inthe presence of the at least one polyvalent antimony compound issubstantially free of iron chloride, iron metal, and/ortrialkylphosphate. In some embodiments, the heating of the1,1,1,3,3-pentachloropropane in the presence of the at least onepolyvalent antimony compound is conducted in the presence of less thanabout 5 weight percent of iron chloride, iron metal, and/ortrialkylphosphate, on a basis of weight of chlorinated alkane substrate.In some embodiments, the heating of the 1,1,1,3,3-pentachloropropane inthe presence of the at least one polyvalent antimony compound isconducted in the presence of less than about 1 weight percent of ironchloride, iron metal, and/or trialkylphosphate, on a basis of weight ofchlorinated alkane substrate. In some embodiments, the heating of the1,1,1,3,3-pentachloropropane in the presence of the at least onepolyvalent antimony compound is conducted in the presence of less thanabout 0.1 weight percent of iron chloride, iron metal, and/ortrialkylphosphate, on a basis of weight of chlorinated alkane substrate.In some embodiments, the heating of the 1,1,1,3,3-pentachloropropane inthe presence of the at least one polyvalent antimony compound comprisinga pentavalent antimony compound to thereby form a product comprisingsaid alkene product is conducted in the absence of iron chloride, ironmetal, and/or trialkylphosphate. In some embodiments, the heating of the1,1,1,3,3-pentachloropropane is conducted in the presence of the atleast one polyvalent antimony compound as the sole catalyst present inthe reaction.

In some embodiments, there is provided a method of recycling at leastone polyvalent antimony catalyst from a product of a chloroalkanedehydrochlorination process, comprising: (a) providing a productcomprising 1,1,3,3-tetrachloropropene, 1,1,1,3,3-pentachloropropane andat least one polyvalent antimony catalyst, and optionally1,1,1,2,3-pentachloropropane; (b) optionally converting the polyvalentantimony catalyst to trivalent antimony catalyst to form a productcomprising 1,1,3,3-tetrachloropropene, 1,1,1,3,3-pentachloropropane, andat least one trivalent antimony catalyst; (c) separating at least aportion of the 1,1,3,3-tetrachloropropene from: (i) the product of step(a) comprising 1,1,3,3-tetrachloropropene, 1,1,1,3,3-pentachloropropane,and at least one polyvalent antimony catalyst; or (ii) the product ofstep (b) comprising 1,1,3,3-tetrachloropropene,1,1,1,3,3-pentachloropropane, and at least one trivalent antimonycatalyst by distillation; and (d) recycling: (i) a remaining portion ofthe product of step (c)(i) comprising 1,1,1,3,3-pentachloropropane andthe at least one polyvalent antimony catalyst; or (ii) a remainingportion of the product of step (c)(ii) comprising1,1,1,3,3-pentachloropropane and the at least one trivalent antimonycatalyst by distillation; and to a chloroalkane chlorination process ora chloroalkane dehydrochlorination process. Suitable polyvalent antimonycatalysts and trivalent antimony catalysts and other optional componentsare discussed in detail above. Suitable amounts of the components andother optional components are discussed in detail above. Suitableprocessing conditions are discussed in detail above.

In some embodiments, there is provided a method of preparing1,1,3,3-tetrachloropropene by chloroalkane dehydrochlorination process,the method comprising: (a) reacting 1,1,1,3,3-pentachloropropane in thepresence of at least one polyvalent antimony catalyst in a reactionvessel, thereby forming a crude product comprising1,1,3,3-tetrachloropropene, a portion of the1,1,1,3,3-pentachloropropane and the at least one polyvalent antimonycatalyst; and (b) optionally converting the polyvalent antimony catalystto trivalent antimony catalyst to form a product comprising1,1,3,3-tetrachloropropene, 1,1,1,3,3-pentachloropropane, and at leastone trivalent antimony catalyst; (c) separating at least a portion ofthe 1,1,3,3-tetrachloropropene from: (i) the product of step (a)comprising 1,1,3,3-tetrachloropropene, 1,1,1,3,3-pentachloropropane, andat least one polyvalent antimony catalyst; or (ii) the product of step(b) comprising 1,1,3,3-tetrachloropropene, 1,1,1,3,3-pentachloropropane,and at least one trivalent antimony catalyst by distillation; and (d)recycling: (i) a remaining portion of the product of step (c)(i)comprising 1,1,1,3,3-pentachloropropane, and the at least one polyvalentantimony catalyst; or (ii) a remaining portion of the product of step(c)(ii) comprising 1,1,1,3,3-pentachloropropane, and the at least onetrivalent antimony catalyst by distillation; and back to thechloroalkane dehydrochlorination process. Suitable polyvalent antimonycatalysts and trivalent antimony catalysts and other optional componentsare discussed in detail above. Suitable amounts of the components andother optional components are discussed in detail above. Suitableprocessing conditions are discussed in detail above.

In some embodiments, as shown in FIG. 4, there is provided a method ofrecycling at least one polyvalent antimony catalyst from a product of achloroalkane dehydrochlorination process, comprising: (a) providing aproduct comprising at least one chlorinated alkene product, at least onechlorinated alkane product, and at least one polyvalent antimonycatalyst, the at least one chlorinated alkene product having a boilingpoint at least about 5° C. less than the at least one chlorinated alkaneproduct at about 1 atmosphere pressure; (b) optionally converting thepolyvalent antimony catalyst to trivalent antimony catalyst to form aproduct comprising at least one chlorinated alkene product, at least onechlorinated alkane product, and at least one trivalent antimonycatalyst; (c) separating at least a portion of the at least onechlorinated alkene product from: (i) the product of step (a) comprisingat least one chlorinated alkene product, at least one chlorinated alkaneproduct, and at least one polyvalent antimony catalyst; or (ii) theproduct of step (b) comprising the at least one chlorinated alkeneproduct, at least one chlorinated alkane product, and at least onetrivalent antimony catalyst by distillation; and (d) recycling: (i) aremaining portion of the product of step (c)(i) comprising at least onechlorinated alkane product, and the at least one polyvalent antimonycatalyst; or (ii) a remaining portion of the product of step (c)(ii)comprising the at least one chlorinated alkane product, and the at leastone trivalent antimony catalyst to a chloroalkane chlorination processor a chloroalkane dehydrochlorination process. Suitable chlorinatedalkane products, chlorinated alkene products, polyvalent antimonycatalysts and trivalent antimony catalysts and other optional componentsare discussed in detail above. Suitable amounts of the components andother optional components are discussed in detail above. Suitableprocessing conditions are discussed in detail above.

In some embodiments, the chlorinated alkane product is1,1,1,2,3-pentachloropropane and/or 1,1,1,3,3-pentachloropropane, and/orhexachloroethane, 1,1,2,3,3-pentachloropropane, and/or1,1,1,2,2,3-hexachlorobutane.

In some embodiments, the chlorinated alkene product is1,1,3-trichloropropene, 1,1,3,3-tetrachloropropene, and1,1,2,3-tetrachloropropene.

In some embodiments, the polyvalent antimony compound comprises thepentavalent antimony compound and optionally a trivalent antimonycompound, the pentavalent antimony compound comprising one or morepentavalent antimony compounds represented by the following Formula (I),Sb(R¹)_(a)(Cl)_(b)  (I)

-   -   wherein the sum of a and b is 5, provided that b is at least 2,        and    -   R¹ independently for each a is selected from the group        consisting of linear, branched, or cyclic alkyl, and aryl, and    -   the trivalent antimony compound comprising one or more trivalent        antimony compounds represented by the following Formula (II),        Sb(R²)_(c)(Cl)_(d)  (II)    -   wherein the sum of c and d is 3, and    -   R² independently for each c is selected from the group        consisting of linear, branched, or cyclic alkyl, and aryl.

In some embodiments, the trivalent antimony compound is selected fromthe group consisting of antimony trichloride, trialkyl antimony, triarylantimony, and combinations of two or more thereof. In some embodiments,the pentavalent antimony compound is supported on a solid support.

In some embodiments, there is provided a method of preparing achlorinated alkene product by chloroalkane dehydrochlorination process,the method comprising: (a) reacting at least one chlorinated alkane inthe presence of at least one polyvalent antimony catalyst in a reactionvessel, thereby forming a crude product comprising at least onechlorinated alkene product, a portion of the at least one chlorinatedalkane and the at least one polyvalent antimony catalyst, the at leastone chlorinated alkene product having one less chloro group (or chlorineatom) covalently bonded thereto and one less hydrogen atom covalentlybonded thereto than the at least one chlorinated alkane, the at leastone chlorinated alkane and the at least one chlorinated alkene producthaving a carbon backbone structure that is in each case the same, the atleast one chlorinated alkene product having a boiling point at leastabout 5° C. less than the at least one chlorinated alkane; and (b)optionally converting the polyvalent antimony catalyst to trivalentantimony catalyst to form a product comprising at least one chlorinatedalkene product, at least one chlorinated alkane, and at least onetrivalent antimony catalyst; (c) separating at least a portion of the atleast one chlorinated alkene product from: (i) the product of step (a)comprising at least one chlorinated alkene product, at least onechlorinated alkane, and at least one polyvalent antimony catalyst; or(ii) the product of step (b) comprising the at least one chlorinatedalkene product, at least one chlorinated alkane, and at least onetrivalent antimony catalyst by distillation; and (d) recycling: (i) aremaining portion of the product of step (c)(i) comprising at least onechlorinated alkane, and the at least one polyvalent antimony catalyst;or (ii) a remaining portion of the product of step (c)(ii) comprisingthe at least one chlorinated alkane, and the at least one trivalentantimony catalyst by distillation; and back to the chloroalkanedehydrochlorination process; (e) optionally, the trivalent antimonycontained in the chlorinated alkane can be converted to pentavalentantimony by the addition of chlorinating agent such chlorine gas priorto its use as a catalyst in the chlorination of hydrocarbons and/or thecracking of halohydrocarbons. Suitable chlorinated alkane products,chlorinated alkene products, polyvalent antimony catalysts and trivalentantimony catalysts and other optional components are discussed in detailabove. Suitable amounts of the components and other optional componentsare discussed in detail above. Suitable processing conditions arediscussed in detail above.

In some embodiments, the at least one chlorinated alkane is reacted witha source of ferric chloride in the presence of the at least onepolyvalent antimony catalyst in a reaction vessel.

In some embodiments, wherein the reacting at least one chlorinatedalkane in the presence of at least one polyvalent antimony catalyst in areaction vessel, thereby forming a crude product comprising at least onechlorinated alkene product, a portion of the at least one chlorinatedalkane and the at least one polyvalent antimony catalyst issubstantially free of iron chloride, iron metal, and/ortrialkylphosphate.

In some embodiments, the reacting at least one chlorinated alkane in thepresence of at least one polyvalent antimony catalyst in a reactionvessel, thereby forming a crude product comprising at least onechlorinated alkene product, a portion of the at least one chlorinatedalkane and the at least one polyvalent antimony catalyst is conducted inthe presence of less than about 5 weight percent of iron chloride, ironmetal, and/or trialkylphosphate, on a basis of weight of chlorinatedalkane substrate. In some embodiments, the reacting at least onechlorinated alkane in the presence of at least one polyvalent antimonycatalyst in a reaction vessel, thereby forming a crude productcomprising at least one chlorinated alkene product, a portion of the atleast one chlorinated alkane and the at least one polyvalent antimonycatalyst is conducted in the presence of less than about 1 weightpercent of iron chloride, iron metal, and/or trialkylphosphate, on abasis of weight of chlorinated alkane substrate. In some embodiments,the reacting at least one chlorinated alkane in the presence of at leastone polyvalent antimony catalyst in a reaction vessel, thereby forming acrude product comprising at least one chlorinated alkene product, aportion of the at least one chlorinated alkane and the at least onepolyvalent antimony catalyst is conducted in the presence of less thanabout 0.1 weight percent of iron chloride, iron metal, and/ortrialkylphosphate, on a basis of weight of chlorinated alkane substrate.In some embodiments, the reacting at least one chlorinated alkane in thepresence of at least one polyvalent antimony catalyst in a reactionvessel, thereby forming a crude product comprising at least onechlorinated alkene product, a portion of the at least one chlorinatedalkane and the at least one polyvalent antimony catalyst is conducted inthe absence of iron chloride, iron metal, and/or trialkylphosphate. Insome embodiments, the reacting at least one chlorinated alkane in thepresence of at least one polyvalent antimony catalyst in a reactionvessel, thereby forming a crude product comprising at least onechlorinated alkene product, a portion of the at least one chlorinatedalkane and the at least one polyvalent antimony catalyst is conducted inthe presence of the at least one polyvalent antimony compound as thesole catalyst present in the reaction.

In some embodiments, the chlorinated alkane is1,1,1,2,3-pentachloropropane. In some embodiments, the chlorinatedalkane is hexachloroethane, 1,1,2,3,3-pentachloropropane, and/or1,1,1,2,2,3-hexachlorobutane.

In some embodiments, the chlorinated alkene is 1,1,3-trichloropropene,1,1,3,3-tetrachloropropene, and 1,1,2,3-tetrachloropropene.

In some embodiments, the at least one chlorinated alkene productcomprises 1,1,3,3-tetrachloropropene. In some embodiments, the at leastone chlorinated alkene product comprises 1,1,2,3-tetrachloropropene.

In some embodiments, the polyvalent antimony compound comprises thepentavalent antimony compound and optionally a trivalent antimonycompound, the pentavalent antimony compound comprising one or morepentavalent antimony compounds represented by the following Formula (I),Sb(R¹)_(a)(Cl)_(b)  (I)

-   -   wherein the sum of a and b is 5, provided that b is at least 2,        and    -   R¹ independently for each a is selected from the group        consisting of linear, branched, or cyclic alkyl, and aryl, and    -   the trivalent antimony compound comprising one or more trivalent        antimony compounds represented by the following Formula (II),        Sb(R²)_(c)(Cl)_(d)  (II)    -   wherein the sum of c and d is 3, and    -   R² independently for each c is selected from the group        consisting of linear, branched, or cyclic alkyl, and aryl.

In some embodiments, the trivalent antimony compound is selected fromthe group consisting of antimony trichloride, trialkyl antimony, triarylantimony, and combinations of two or more thereof.

The present invention is more particularly described in the examplesthat follow, which are intended to be illustrative only, since numerousmodifications and variations therein will be apparent to those skilledin the art.

EXAMPLES Example 1

Present Example 1 demonstrates a non-limiting embodiment of the presentinvention, in which 1,1,1,2,3-pentachloropropane was prepared underbatch conditions, using antimony pentachloride (SbCl₅) as a catalyst.

To a 250 milliliter (mL) three-necked round bottom flask was charged1,1,1,3-tetrachloropropane (147.1 grams) and antimony pentachloride (0.5mL). The 250 mL three-necked round bottom flask was equipped with achlorine inlet, magnetic stirring bar, 18 inch (45.72 cm) Vigreux columnand a gas outlet, which was connected to a sodium hydroxide scrubber.The reaction flask was wrapped with insulating cloth to protect thereaction from ultraviolet light in order to suppress any free-radicalchlorination that might occur. The amount of antimony pentachloride usedrepresented 0.80 weight percent based on the amount of thetetrachloropropane reactant. The reaction mixture in the flask washeated to 70° C. by means of a heating mantle. Chlorine gas at 20° C.was added below the surface of the reaction mixture at a rate ofapproximately 0.32 grams per minute for three hours. Thereafter, thechlorine feed was stopped and the reaction vessel degassed withnitrogen. The crude reaction mixture was analyzed by means of gaschromatography (GC). The analysis showed the reaction mixture to contain1,1,1,2,3-pentachloropropane with 81.3% selectivity, and 5 weightpercent of 1,1,1,3-tetrachloropropane. The percent conversion of thetetrachloropropane reactant was calculated to be 95.1 percent.

Example 2

Present Example 2 demonstrates a non-limiting embodiment of the presentinvention, in which 1,1,1,2,3-pentachloropropane was prepared underbatch conditions, using antimony trichloride (SbCl₃) as a precursor ofantimony pentachloride (SbCl₅).

The procedure of Example 1 was followed, except that 143.5 grams of1,1,1,3-tetrachloropropane was used, 0.90 grams of antimony trichloridewas used (0.63 weight percent catalyst) and the reaction mixture washeated to 120° C. by means of the heating mantle. After three hours ofchlorine feed, the flow of chlorine was stopped and the reaction vesseldegassed with nitrogen. The crude reaction mixture (159.5 grams) wasanalyzed by GC and found to contain 1,1,1,2,3-pentachloropropaneproduced with 89% selectivity and 0.001 weight percent of1,1,1,3-tetrachloropropane. The percent conversion of thetetrachloropropane reactant was calculated to be essentially 100percent.

Example 3

Present Example 3 demonstrates a non-limiting embodiment of the presentinvention, in which 1,1,1,2,3-pentachloropropane was prepared underbatch conditions, using triphenyl antimony (Sb(C₆Hs)₃) as a precursor oftriphenyl antimony dichloride ((C₆Hs)₃SbCl₂).

The procedure of Example 2 was followed except that 0.5 grams oftriphenyl antimony was used (0.35 weight % of catalyst), and thechlorine was added over 5.5 hours. After completing the chlorineaddition, the reaction vessel was degassed with nitrogen. The crudereaction mixture was analyzed by GC and found to contain1,1,1,2,3-pentachloropropane produced with 81.2% selectivity. Thepercent conversion of the tetrachloropropane reactant was calculated tobe essentially 100 percent.

Comparative Example 1

Present Comparative Example 1 was conducted in comparison to Example 1above. In present Comparative Example 1, anhydrous ferric chloride wasused as the catalyst in the absence of a polyvalent antimony compound,such as antimony pentachloride.

The procedure of Example 1 was followed except that anhydrous ferricchloride (0.64 grams) was used as the catalyst (0.45 weight percent ofcatalyst), and the reaction mixture was heated to 70° C. The chlorinefeed (at 20° C.) was added over 2.25 hours. At the end of this time, thechlorine feed was stopped and the reaction vessel was degassed withnitrogen. The crude reaction mixture (132.4 grams) was analyzed by GCand found to contain 1,1,1,2,3-pentachloropropane produced with 58.7%selectivity, and 0.039 weight percent of 1,1,1,3-tetrachloropropane. Thepercent conversion of the tetrachloropropane was calculated to be 99.9percent.

Example 4

Present Example 4 demonstrates a non-limiting embodiment of the presentinvention, in which 1,1,1,2,3-pentachloropropane was prepared undercontinuous conditions.

A feed solution of antimony trichloride (8.94 grams, 0.8 wt % SbCl₅equivalent) and 1,1,1,3-tetrachloropropane (1,458.2 grams) was preparedby stirring the reagents with a magnetic stir bar in a one literErlenmeyer flask for 30 minutes.

To a 600-mL Nickel 200 autoclave was charged 230.9 grams of the feedsolution. The contents of the autoclave were pressurized to 100 psigwith nitrogen, heated to 80° C., and chlorine gas was introduced beneaththe liquid surface when the temperature reached 80° C. After two hoursof chlorine gas addition at 100 psig, additional feed solution (584.2grams) was pumped into the autoclave at an overall average rate of 2.01g/min. Chlorine gas addition (167 grams total) was continuouslyperformed for a total of 410 minutes. A product mixture and HCl wereremoved via a dip tube with backpressure regulator to maintain a liquidlevel of about 180 mL in the autoclave and a pressure of about 100 psig.Upon shutdown, 795.7 grams of crude product mixture had been collected,and was determined by GC analysis to contain 54.8 wt %1,1,1,2,3-pentachloropropane and 44.3 wt % 1,1,1,3-tetrachloropropane.Overall conversion was 51.2% with a selectivity of 99.1% to1,1,1,2,3-pentachloropropane.

Example 5

Present Example 5 demonstrates a non-limiting embodiment of the presentinvention, in which 1,1,2,3-tetrachloropropene was prepared by way of atwo-stage (first reaction-second reaction) serial batch process.

In a first reaction, 1,1,1,3-tetrachloropropane (143.5 grams) wascharged to a 250 mL three-necked round bottom flask equipped with athermocouple, magnetic stirring bar, chlorine inlet and an 18 inch(45.72 cm) Vigreux condenser connected to a sodium hydroxide scrubber.The tetrachloropropane was heated to 120° C. by means of a heatingmantle, and 0.05 mL of antimony pentachloride was added to it. Themixture was magnetically stirred for one minute and then chlorine wasintroduced beneath the surface of the reaction mixture for 16 hours.After 13.66 hours had elapsed, an additional charge of antimonypentachloride (0.20 mL) was added to the reaction mixture, and thechlorine flow was continued. After the 16 hours of chlorine addition,the flow of chlorine was stopped. A crude 1,1,1,2,3-pentachloropropaneproduct mixture was obtained containing 87.59 wt %1,1,1,2,3,-pentachloropropane and no detectable1,1,1,3-tetrachloropropane.

In a second reaction, the crude 1,1,1,2,3-pentachloropropane productmixture of the first reaction was cooled to 20° C. with nitrogendegassing to remove any excess chlorine. The cooled crude productmixture was then charged with 0.60 grams of anhydrous ferric chloride,so as to form a second reaction mixture, which was heated to 165° C. fortwo hours. Upon reaching a temperature of 123° C., the second reactionmixture evolved a copious amount of gas, as evidenced by bubbling in thesodium hydroxide scrubber. At the end of two hours, the resultingsubsequent crude reaction product was cooled and analyzed by GC. It wasfound to contain 78.80 wt % 1,1,2,3-tetrachloropropene produced with86.2% selectivity, and 0.03 weight percent of1,1,1,2,3-pentachloropropane.

Comparative Example 2

Present Comparative Example 2 was conducted in comparison to the secondreaction of Example 5 above.

A mixture of 1,1,1,2,3-pentachloropropane (66.0 grams) and anhydrousferric chloride (0.10 grams) was charged to a 250 mL three-necked roundbottom flask equipped with a condenser, thermocouple, mechanical stirrerand a gas outlet, which was connected to a water scrubber. The amount offerric chloride catalyst used was 0.15 weight percent. The reactionmixture was heated over two days as follows: 150° C. for 2.25 hours,cooled to room temperature and stored under nitrogen, overnight, 160° C.for 3.17 hours, and 164° C. for 2.75 hours. The heating times asrecited, include the time required to reach the new setpoint, eitherfrom room temperature or the previous setpoint. The reaction mixture wascooled and then flash vacuum distilled at pot temperatures ranging from64° C. to 85° C. and a pressure of 120 Torr. The distillate (46.5 grams)was analyzed by GC and found to contain 1,1,2,3-tetrachloropropeneproduced with 98.7% selectivity and at an overall yield of 84.7 percent.It also contained 0.6 weight percent of 1,1,1,2,3-pentachloropropane.The percent conversion of the pentachloropropane reactant was calculatedto be 99.4 percent.

Example 6

Present Example 6 demonstrates a non-limiting embodiment of the presentinvention, in which 1,1,2,3-tetrachloropropene was prepared under batchconditions from 1,1,1,2,3-pentachloropropane using a combination offerric chloride and antimony pentachloride as the catalyst.

Fifty grams (50 g) of 1,1,1,2,3-pentachloropropane (having a purity of96.94 wt %) and 0.1614 g of anhydrous ferric chloride (obtained fromFisher Scientific), and 25 microliters (μL) of antimony pentachloride(containing 0.059 g of antimony pentachloride, obtained from Aldrich)were combined in a 100-mL three-necked round-bottom flask equipped witha magnetic stirring bar, condenser attached to a water scrubber,thermocouple, and a heating mantle. The mixture was stirred and heatedfrom room temperature to 165° C. Upon reaching 130° C., copious amountsof gas were evolved to the water scrubber and continued throughout theremainder of the experiment. After three hours, the mixture was cooledto room temperature and then sampled for gas chromatography analysis.The product was determined by GC analysis to contain 80.19 wt % of1,1,2,3-tetrachloropropene and 16.74 wt % of1,1,1,2,3-pentachloropropane, indicating a molar conversion of 85.1%.

Comparative Example 3

Present Comparative Example 3 provides a description of the batchpreparation of 1,1,2,3-tetrachloropropene from1,1,1,2,3-pentachloropropane using only ferric chloride as the catalyst.

Fifty grams (50 g) of 1,1,1,2,3-pentachloropropane (having a purity of96.21 wt %) and 0.1676 g of anhydrous ferric chloride (obtained fromFisher Scientific) were combined in a 100-mL three-necked round-bottomflask equipped with a magnetic stirring bar, condenser attached to awater scrubber, thermocouple, and a heating mantle. The mixture wasstirred and heated from room temperature to 165° C. After three hours,the mixture was cooled to room temperature and then sampled for GCanalysis. The product was determined by GC analysis to contain 44.41 wt% of 1,1,2,3-tetrachloropropene and 52.40 wt % of1,1,1,2,3-pentachloropropane, indicating a molar conversion of 50.4%).

Comparative Example 4

Present Comparative Example 4 provides a description of the batchpreparation of 1,1,2,3-tetrachloropropene from1,1,1,2,3-pentachloropropane using only ferric chloride as the catalyst.

Twenty grams (20 g) of 1,1,1,2,3-pentachloropropane (having a purity of96.21 wt %) and 0.20 g of anhydrous ferric chloride (obtained fromFisher Scientific) were combined a 50-mL round-bottom flask equippedwith a Claisen adapter, thermocouple, magnetic stirring bar, condenserattached to a water scrubber, and a heating mantle. The mixture wasstirred and heated over two days as follows: 100° C. (3.85 hrs) then110° C. (1.73 hrs); cooled to room temperature and stored over theweekend under nitrogen, 130° C. (1.50 hrs) then 150° C. (5.45 hrs). Theheating times, as recited, include the time required to reach the newsetpoint, either from room temperature or the previous setpoint. Themixture (14.9 g) was cooled to room temperature and then sampled for GCanalysis. The product was determined by GC analysis to contain 99.35 wt% of 1,1,2,3-tetrachloropropene and 0.30 wt % of1,1,1,2,3-pentachloropropane, indicating a conversion of 99.56% byweight (with regard to the starting amount of1,1,1,2,3-pentachloropropane).

The following Table 1 provides a summary of Comparative Examples 2 and4, and Example 4, for purposes of demonstrating the combination ofdesirable reaction time and conversion provided by the method of thepresent invention with regard to preparing 1,1,2,3-tetrachloropropenefrom 1,1,1,2,3-pentachloropropane using a combination of ferric chlorideand antimony pentachloride as catalyst (Example 4) compared to usingferric chloride alone as the catalyst (Comparative Examples 2 and 4).

TABLE 1 Temper- Catalyst ature, Time Conversion, Example Catalystloading⁽¹⁾ ° C.⁽²⁾ Heated⁽³⁾ %⁽⁴⁾ Comp 4 FeCl₃ 1 wt % 150 12.53 hrs99.56 Comp 2 FeCl₃ 0.15 wt % 164 8.17 hrs 99.40 4⁽⁵⁾ FeCl₃ 0.30 wt % 1652 hrs 99.99 SbCl₅ 0.41 wt % ⁽¹⁾Catalyst loading is based on weight of1,1,1,2,3-pentachloropropane. ⁽²⁾The term “Temperature, ° C.” means themaximum temperature of the reaction. ⁽³⁾The term “Time Heated” means thetime from activation of the heating mantle to removal of the heatingmantle from the reaction vessel. ⁽⁴⁾The percent conversion wasdetermined by gas chromatography analysis. ⁽⁵⁾The second reaction ofExample 4.

The Following Table 2 provides a summary of Comparative Example 3 andExample 6 for purposes of demonstrating the combination of desirablereaction time and conversion provided by the method of the presentinvention with regard to preparing 1,1,2,3-tetrachloropropene from1,1,1,2,3-pentachloropropane using a combination of ferric chloride andantimony pentachloride as catalyst (Example 6) compared to using ferricchloride alone as the catalyst (Comparative Example 3), when thereactions are conducted at the same temperature (i.e., 165° C.), time(i.e., 3 hours), and catalyst loading (i.e., 0.33 wt % total).

TABLE 2 Temper- Catalyst ature, Time Conversion, Example Catalystloading⁽¹⁾ ° C.⁽²⁾ Heated⁽³⁾ %⁽⁴⁾ Comp 3 FeCl₃ 0.33 wt % 165 3 hrs 50.56 FeCl3 0.32 wt % 165 3 hrs 85.2 SbCl5 0.10 wt % ⁽¹⁾,⁽²⁾,⁽³⁾, and ⁽⁴⁾areas described with regard to TABLE 1.

Example 7

Present Example 7 demonstrates a non-limiting embodiment of the presentinvention, in which 1,1,2,3-tetrachloropropene was prepared undercontinuous conditions.

To a 250-mL three-necked round bottom flask was charged crude1,1,1,2,3-pentachloropropane (157.8 grams, having a volume of about 100mL, 98.4 wt % containing 0.46 wt % SbCl₅) and anhydrous ferric chloride(0.1730 grams). The 250-mL three-necked round bottom flask was equippedwith a mechanical stirrer, addition funnel, Claisen adapter,thermocouple, and a distillation apparatus (which included adistillation head, condenser, and distillation receiver). Gases exitingthe condenser were directed into a vacuum pump which discharged into awater scrubber. The three-necked round bottom flask and distillationapparatus were placed under vacuum (650 Torr) and heated via a heatingmantle to 164-169° C. pot temperature. After about 80% conversion wasachieve (as determined by measured weight gain in the water scrubber),additional crude 1,1,1,2,3-pentachloropropane (486.0 grams, having avolume of about 300 mL) was added dropwise to the contents of thethree-necked round bottom flask over 271 minutes to maintain a constantpot level while collecting crude 1,1,2,3-tetrachloropropene distillatefrom the distillation apparatus. A total of 376.5 grams of crudedistillate product was collected, and determined (by GC analysis) tocontain 92.9 wt % 1,1,2,3-tetrachloropropene and 6.5 wt %1,1,1,2,3-pentachloropropane. The average residence time was 90 min (100mL/(300 mL/271 min)).

Examples 8-10

The present Examples 8-10 demonstrate non-limiting embodiments of thepresent invention, in which crude 1,1,2,3-tetrachloropropene wasprepared continuously under varying conditions. The procedure of Example7 was followed, with the ferric chloride charge being modified. Reactorpressure was adjusted to change the temperature of the reactor, whilestill maintaining a constant pot level. Results of the experiment aresummarized in the following Table 3.

TABLE 3 Catalyst Catalyst 1,1,2,3- Loading Loading Temper- Residencetetrachloro- wt % Wt % ature Pressure Time propene Example FeCl₃ ⁽⁶⁾SbCl₅ ⁽⁷⁾ (° C.)⁽⁸⁾ (Torr)⁽⁹⁾ (minutes⁾⁽¹⁰⁾ (wt %)⁽¹¹⁾ 8 0.30 0.46 165.0650 102 93.5 9 0.10 0.46 117.5 100 96 68.9 10 0.28 0.46 120.0 100 8470.4 ⁽⁶⁾Based on weight of crude 1,1,1,2,3-pentachloropropane in theinitial charge. ⁽⁷⁾Analyzed concentration in crude1,1,1,2,3-pentachloropropane. ⁽⁸⁾Average temperature at which thereaction was conducted. ⁽⁹⁾Average pressure at which the reaction wasconducted. ⁽¹⁰⁾Average residence time, which was calculated inaccordance with the equation shown in Example 7 herein. ⁽¹¹⁾Based on thetotal weight of crude distillate product collected.

Example 11

Present Example 11 demonstrates a non-limiting embodiment of the presentinvention, in which a crude 1,1,2,3-tetrachloropropene product, that wasprepared in accordance with Examples 4, 7, 8, 9, and 10, was distilled.About 10 percent of the crude 1,1,2,3-tetrachloropropene product wasprepared in accordance with Example 4, and about 90 percent by weight ofthe crude 1,1,2,3-tetrachloropropene product was prepared in accordancewith Examples 7, 8, 9, and 10, the percent weights in each case beingbased on the total weight of the crude 1,1,2,3-tetrachloropropeneproduct.

A distillation apparatus was assembled using the following components: a500-mL three-necked round bottom flask (which operated as a reboiler); a10-tray, 2.54 cm Oldershaw vacuum-jacketed distillation column; a 2.54cm Oldershaw vacuum-jacketed feed port; a 2.54 cm Oldershawvacuum-jacketed packed section containing 115 cm of 0.16″ Pro-Pak™protruded Nickel packing; a swinging bucket product takeoff connected toa reflux timer, and a water-cooled condenser. The distillation apparatuswas heated with a heating mantle controlled by a Variac voltageregulator.

The distillation apparatus was held at 100 Torr using a vacuum pump witha pressure controller. Over a period of 16 hours using a peristalticpump, 2.15 kilograms (kg) of crude 1,1,2,3-tetrachloropropene productwas pumped into the column of the distillation apparatus at the feedport, located between the Oldershaw and packed column sections. Thecrude 1,1,2,3-tetrachloropropene was prepared in accordance with someembodiments of the present invention and was determined, by GC analysis,to contain 81.0 wt % 1,1,2,3-tetrachloropropene, 17.7 wt %1,1,1,2,3-pentachloropropane, 0.29 wt % SbCl₃, and 0.9 wt % ofunidentified impurities. A distillate product, in an amount of 1.61 kg,was collected at a reflux ratio of 2:1. Bottoms were allowed toaccumulate in the reboiler. Once feed pumping and product collectionwere stopped, the reflux ratio was dropped to 1:1, and 0.15 kg ofadditional distillate was collected. A residue, in an amount of 0.29 kg,remained in the reboiler.

The distillate product was determined, by GC analysis, to contain 99.65wt % 1,1,2,3-tetrachloropropene, and by Inductively Coupled Plasma (ICP)analysis to contain antimony in an amount of less than 10 ppmw (partsper million by weight). The reboiler residue was determined, by GCanalysis, to contain 94.6 wt % 1,1,1,2,3-pentachloropropane, and lessthan 0.1 wt % 1,1,2,3-tetrachloropropene, and by ICP analysis to contain0.84 wt % antimony. Wet chemical analysis for antimony trichlorideshowed: less than 0.02 wt % of antimony trichloride in the distillateproduct; 0.66 wt % of antimony trichloride in the additional distillate;and 1.3 wt % antimony trichloride in the reboiler residue.

Example 12

Present Example 12 demonstrates a non-limiting embodiment of the presentinvention, in which reboiler residue containing antimony trichloride wasrecycled and used to form 1,1,1,2,3-pentachloropropane.

An aliquot (having a volume of about 50 mL) of the reboiler residue fromExample 11 was passed through a syringe filter to remove a minor amountof solids. The resulting filtrate, in an amount of 67.53 grams(containing 1.10 wt % antimony trichloride), was mixed with 51.29 grams1,1,1,3-tetrachloropropane (99% purity) to prepare a feed solutioncontaining 0.64 wt % antimony trichloride. The feed solution wasdetermined by GC analysis to contain 47.5 wt %1,1,1,3-tetrachloropropane and 49.5 wt % 1,1,1,2,3-pentachloropropane.

The feed solution was charged to a 250-mL three-necked flask equippedwith a thermocouple, magnetic stir-bar, chlorine sparger, and a 18″(45.72 cm) Vigreux condenser connected to a deionized water scrubber.The feed solution was heated to 100° C. using a Variac-controlledheating mantle attached to a temperature controller. A chlorine gas feedinto the 250-mL three-necked flask was started when the temperaturereached 70° C. Chlorine breakthrough was observed about 11 minutes intothe run (after the chlorine gas feed was started). The chlorine gas flowrate was reduced and the breakthrough subsided. The chlorine gas feedwas later returned to the initial higher flow rate without anyadditional breakthrough being observed. Chlorine gas in an amounttotaling about 24.5 grams was fed to the 250-mL three-necked flask overa period of 4.3 hours. Hydrogen chloride, in an amount totaling 10.9grams, was recovered in the scrubber. A product, totaling 120.6 grams,was collected and determined, by GC analysis, to contain 95.0 wt %1,1,1,2,3-pentachloropropane and 0.015 wt % 1,1,1,3-tetrachloropropane.

Example 13

A distillation apparatus was assembled using the following components: a250-mL three-necked round bottom flask (which operated as a reboiler); a20-tray, 2.54 cm Oldershaw vacuum-jacketed distillation column; a30-tray 2.54 cm Oldershaw vacuum-jacketed distillation column; aswinging bucket product takeoff connected to a reflux timer; and awater-cooled condenser. The distillation apparatus was heated with aheating mantle controlled by a Variac voltage regulator.

Approximately 240 grams of dehydrohalogenation reactor productcontaining 50.5 area % 1,1,3,3-tetrachloropropene (b.p. 151° C.), 44.56area % 1,1,2,3-tetrachloropropane (b.p. 167° C.), 1.9 area %1,1,1,2,3-pentachloropropane (b.p. 196 C), and 362 ppmw SbCl₃ (by wetchemical titration) was charged to as 250 mL three-neck, round-bottomflask. The distillation apparatus was held at 590 Torr using a vacuumpump with a pressure controller. 77.0 grams of distillate were collectedat a 4:1 reflux ratio. The distillate was determined by GC analysis, tocontain 97.9 area % 1,1,3,3-tetrachloropropene and 0.3 area %1,1,2,3-tetrachloropropene. No SbCl₃ was detected by wet chemicaltitration. 147.3 grams of column and reboiler contents were recovered.This composition, containing 1,1,3,3-tetrachloropropene,1,1,2,3-tetrachloropropene, 1,1,1,2,3-pentachloropropane, and SbCl₃, canbe recycled to a chlorination or dehydrohalogenation process.

The present invention has been described with reference to specificdetails of particular embodiments thereof. However, it is not intendedthat such details be regarded as limitations upon the scope of theinvention except insofar as and to the extent that they are included inthe accompanying claims.

What is claimed is:
 1. A method of preparing a chlorinated alkeneproduct by chloroalkane dehydrochlorination process, the methodcomprising: (a) reacting at least one chlorinated alkane in the presenceof at least one polyvalent antimony catalyst in a reaction vessel,thereby forming a crude product comprising at least one chlorinatedalkene product, a portion of the at least one chlorinated alkane and theat least one polyvalent antimony catalyst, the at least one chlorinatedalkene product having one less chloro group (or chlorine atom)covalently bonded thereto and one less hydrogen atom covalently bondedthereto than the at least one chlorinated alkane, the at least onechlorinated alkane and the at least one chlorinated alkene producthaving a carbon backbone structure that is in each case the same, the atleast one chlorinated alkene product having a boiling point at leastabout 5° C. less than the at least one chlorinated alkane; and (b)optionally converting the polyvalent antimony catalyst to trivalentantimony catalyst to form a product comprising at least one chlorinatedalkene product, at least one chlorinated alkane, and at least onetrivalent antimony catalyst; (c) separating at least a portion of the atleast one chlorinated alkene product from: (i) the product of step (a)comprising at least one chlorinated alkene product, at least onechlorinated alkane, and at least one polyvalent antimony catalyst; or(ii) the product of step (b) comprising the at least one chlorinatedalkene product, at least one chlorinated alkane, and at least onetrivalent antimony catalyst by distillation; and (d) optionally, thetrivalent antimony contained in the chlorinated alkane can be convertedto pentavalent antimony by the addition of chlorinating agent suchchlorine gas prior to its use as a catalyst in the chlorination ofhydrocarbons and/or the cracking of halohydrocarbons.
 2. The method ofclaim 1, wherein the at least one chlorinated alkane is reacted with asource of ferric chloride in the presence of the at least one polyvalentantimony catalyst in a reaction vessel.
 3. The method of claim 1,wherein the reacting at least one chlorinated alkane in the presence ofat least one polyvalent antimony catalyst in a reaction vessel, therebyforming a crude product comprising at least one chlorinated alkeneproduct, a portion of the at least one chlorinated alkane and the atleast one polyvalent antimony catalyst is substantially free of ironchloride, iron metal, and/or trialkylphosphate.
 4. The method of claim1, wherein the reacting at least one chlorinated alkane in the presenceof at least one polyvalent antimony catalyst in a reaction vessel,thereby forming a crude product comprising at least one chlorinatedalkene product, a portion of the at least one chlorinated alkane and theat least one polyvalent antimony catalyst is conducted in the presenceof less than about 5 weight percent of iron chloride, iron metal, and/ortrialkylphosphate, on a basis of weight of chlorinated alkane substrate.5. The method of claim 1, wherein the reacting at least one chlorinatedalkane in the presence of at least one polyvalent antimony catalyst in areaction vessel, thereby forming a crude product comprising at least onechlorinated alkene product, a portion of the at least one chlorinatedalkane and the at least one polyvalent antimony catalyst is conducted inthe presence of less than about 1 weight percent of iron chloride, ironmetal, and/or trialkylphosphate, on a basis of weight of chlorinatedalkane substrate.
 6. The method of claim 1, wherein the reacting atleast one chlorinated alkane in the presence of at least one polyvalentantimony catalyst in a reaction vessel, thereby forming a crude productcomprising at least one chlorinated alkene product, a portion of the atleast one chlorinated alkane and the at least one polyvalent antimonycatalyst is conducted in the presence of less than about 0.1 weightpercent of iron chloride, iron metal, and/or trialkylphosphate, on abasis of weight of chlorinated alkane substrate.
 7. The method of claim1, wherein the reacting at least one chlorinated alkane in the presenceof at least one polyvalent antimony catalyst in a reaction vessel,thereby forming a crude product comprising at least one chlorinatedalkene product, a portion of the at least one chlorinated alkane and theat least one polyvalent antimony catalyst is conducted in the absence ofiron chloride, iron metal, and/or trialkylphosphate.
 8. The method ofclaim 1, wherein the reacting at least one chlorinated alkane in thepresence of at least one polyvalent antimony catalyst in a reactionvessel, thereby forming a crude product comprising at least onechlorinated alkene product, a portion of the at least one chlorinatedalkane and the at least one polyvalent antimony catalyst is conducted inthe presence of the at least one polyvalent antimony compound as thesole catalyst present in the reaction.
 9. The method of claim 1, whereinthe chlorinated alkane is 1,1,1,2,3-pentachloropropane.
 10. The methodof claim 1, wherein the chlorinated alkane is1,1,1,3,3-pentachloropropane, 1,1,1,3-tetrachloropropane,1,1,2,3,3-pentachloropropane, and/or 1,1,1,2,2,3-hexachlorobutane. 11.The method of claim 1, wherein the chlorinated alkene is1,1,3-trichloropropene, 1,1,3,3-tetrachloropropene, and1,1,2,3-tetrachloropropene.
 12. The method of claim 1, wherein the atleast one chlorinated alkene product comprises1,1,3,3-tetrachloropropene.
 13. The method of claim 1, wherein the atleast one chlorinated alkene product comprises1,1,2,3-tetrachloropropene.
 14. The method of claim 1, wherein thepolyvalent antimony compound comprises the pentavalent antimony compoundand optionally a trivalent antimony compound, the pentavalent antimonycompound comprising one or more pentavalent antimony compoundsrepresented by the following Formula (I),Sb(R¹)_(a)(Cl)_(b)  (I) wherein the sum of a and b is 5, provided that bis at least 2, and R¹ independently for each a is selected from thegroup consisting of linear, branched, or cyclic alkyl, and aryl, and thetrivalent antimony compound comprising one or more trivalent antimonycompounds represented by the following Formula (II),Sb(R²)_(c)(Cl)_(d)  (II) wherein the sum of c and d is 3, and R²independently for each c is selected from the group consisting oflinear, branched, or cyclic alkyl, and aryl.
 15. The method of claim 1,wherein the trivalent antimony compound is represented by Formula (II)Sb(R²)_(c)(Cl)_(d)  (II) wherein the sum of c and d is 3, and R²independently for each c is selected from the group consisting oflinear, branched, or cyclic alkyl, and aryl.
 16. The method of claim 1,wherein the trivalent antimony compound is selected from the groupconsisting of antimony trichloride, trialkyl antimony, triaryl antimony,and combinations of two or more thereof.
 17. A method of preparing1,1,3,3-tetrachloropropene by chloroalkane dehydrochlorination process,the method comprising: (a) reacting 1,1,1,3,3-pentachloropropane in thepresence of at least one polyvalent antimony catalyst in a reactionvessel, thereby forming a crude product comprising1,1,3,3-tetrachloropropene, a portion of the1,1,1,3,3-pentachloropropane and the at least one polyvalent antimonycatalyst; and (b) optionally converting at least a portion of thepolyvalent antimony catalyst to trivalent antimony catalyst to form aproduct comprising 1,1,3,3-tetrachloropropene,1,1,1,3,3-pentachloropropane, and at least one trivalent antimonycatalyst; (c) separating at least a portion of the1,1,3,3-tetrachloropropene from: (i) the product of step (a) comprising1,1,3,3-tetrachloropropene, 1,1,1,3,3-pentachloropropane, and at leastone polyvalent antimony catalyst; or (ii) the product of step (b)comprising 1,1,3,3-tetrachloropropene, 1,1,1,3,3-pentachloropropane, andat least one trivalent antimony catalyst by distillation.